Synthesis and Application in Catalysis of Planar Chiral - American

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Synthesis and Application in Catalysis of Planar Chiral (η5-Cyclohexadienyl)tricarbonylmanganese-Based Ligands Franc-oise Rose-Munch,*,† Derya Cetiner,† Murielle Chavarot-Kerlidou,† Eric Rose,*,† Francine Agbossou-Niedercorn,‡ Lise-Marie Chamoreau,§ and Geoffrey Gontard§ †

UPMC Univ Paris 6, Institut Parisien de Chimie Moleculaire, CNRS UMR 7201, Equipe Chimie Organique and Organometallique, 4 place Jussieu, 75005 Paris Cedex 05, France ‡ USTL, ENSCL, CNRS UMR 8181, 59655 Villeneuve d’Ascq, France § UPMC Univ Paris 6, Institut Parisien de Chimie Moleculaire, CNRS UMR 7201, Centre de Resolution de Structures, 4 place Jussieu, 75005 Paris Cedex 05, France

bS Supporting Information ABSTRACT: Mono- and bidentate ligands (58, 1518, 20, 2931) have been synthesized in which the phosphinyl group substitutes a (η5-cyclohexadienyl)Mn(CO)3 scaffold. In the case of one of the bidentate ligands, 15, the formation of the corresponding Pd complex was studied. The complex unexpectedly afforded two bimetallic complexes depending on the solvent of the reaction: the neutral complex 33 and the cationic complex 34, whose X-ray structures were established. The catalysts carrying the new ligands demonstrated high activity (99% conversion) in the palladium-catalyzed allylic substitution. The resolution of three of the ligands, 6, 8, and 15, was achieved, and the catalyst with the enantioenriched PN ligand 15 delivered fairly good enantioselectivity in asymmetric allylic substitution.

1. INTRODUCTION Whereas planar chiral ferrocenes are the best-known examples of organometallic ligands for metal-catalyzed asymmetric reactions,1a tricarbonylmetal-containing chiral complexes are now beginning to play major roles in enantioselective catalysis.1b In such nonmetallocenic structures, the “spectator” organometallic fragment not only generates the planar chirality in the catalytic center environment but may also act as a steric and electronic modulator.2 Most of the examples described in the literature rely on a planar chiral (η6-arene)Cr(CO)3 scaffold.35 Other ligands based on a different tricarbonylmetal tripod are relatively rare and, to our knowledge, are limited to (η5-Cp)Re(CO)3 (cyrhetrene) derivatives,68 to a single example with a (η4-diene)Fe(CO)3 fragment,9 and to (η5-Cp)Mn(CO)3.1014 The latter compounds containing a cyclopentadienyl platform are the only tricarbonylmanganese complexes used as catalysts. Mn complexes such as (η5-cyclohexadienyl)Mn(CO)3 complexes, which could lie somewhere between the (η6-arene)Cr(CO)3 and the cymantrene series, have never been employed for the design of planar chiral ligands. We thought that their originality due, in part, to their special structure with an sp3 carbon lying above the plane of the π system15 as well as electronic properties very close to those of (arene)Cr(CO)3 complexes16 might confer them interesting properties as ligands in catalysis. The easy introduction of chelating functions on the η5 scaffold, such as a PPh2 phosphinyl group, is thus of strategic importance for the development of applications of (η5-cyclohexadienyl)Mn(CO)3 r 2011 American Chemical Society

complexes in catalysis. To our knowledge, up to now, very few η5 complexes substituted by a PPh2 function have been synthesized. The introduction of a phosphinyl group at the sp3 C6 carbon of the cyclohexadienyl unit, which is located exo to the Mn(CO)3 tripod, has been realized by addition of PPh2Li onto the cationic (η6-benzene)Mn(CO)3þ complex17 (complex A, Figure 1). Two other phosphine derivatives, with the phosphinyl substituent localized on the C1 carbon (complexes B) or on the C2 carbon (complex C) of the cyclohexadienyl moiety, were obtained from a chloro-substituted precursor by a palladium-catalyzed crosscoupling procedure for B18 or from a bromo derivative19 by a halogen metal exchange reaction for C.20 Finally, a fourth example (complex D) was recently prepared from an anisole derivative submitted to a lithiationelectrophilic quenching sequence.20 To take advantage of the synthesis of the η5 complexes BD substituted on the π system, it was interesting to generalize the three main methods of functionalization of η5 Mn complexes (Pd cross-coupling reactions,18,21 lithiationelectrophilic quenching sequence,22 and metalhalogen exchange followed by electrophilic trapping19) to the preparation of other examples of monodentate ligands, in particular phosphinyl-substituted η5 complexes with a phenyl group on the sp3 carbon atom. Moreover, it was of interest to try the combination of the different functionalization pathways developed by our group in order to Received: March 16, 2011 Published: June 15, 2011 3530

dx.doi.org/10.1021/om200231p | Organometallics 2011, 30, 3530–3543

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Table 1. Phosphinylation Conditions for Complexes 1 and 2

5

Figure 1. Previous PPh2-substituted (η -cyclohexadienyl)Mn(CO)3 complexes.

entry

substrate

R1

1

1a

H

2

c

H

2

R2

product

yield (%)

H

5a,b

43b

OMe

6

83

C2:C3 70:30 C3 only

a

Conditions: 2 equiv of nBuLi, 2 equiv of TMEDA, reaction time 2 h, then 2.5 equiv of Ph2PCl. b Conversion 70%. c Conditions: 1.6 equiv of nBuLi, 1.6 equiv of TMEDA, reaction time 1 h, then 2 equiv of Ph2PCl.

Scheme 1. Phosphinylation Conditions for Complexes 3 and 4

Figure 2. Monodentate phosphorus ligands and the corresponding (η5-cyclohexadienyl)Mn(CO)3 starting complexes.

achieve the regioselective introduction of various chelating groups around the η5 scaffold, to give a new family of potential bidentate ligands. In this paper, we wish to report the synthesis of a large variety of mono- and bidentate ligands built on diversely substituted (η5cyclohexadienyl)Mn(CO)3 complexes, the coordination properties of some of them, and their application in enantioselective catalysis. Part of this work has been the subject of a preliminary communication.23

2. RESULTS AND DISCUSSION 2.1. Synthesis of Monodentate Phosphorus-Based Ligands. With the manganese complexes 14 as starting materi-

als, the synthesis of monodentate phosphorus-based ligands 58 gathered in Figure 2 relies on a lithiationelectrophilic quenching sequence, using PPh2Cl as the electrophile. Depending on the position which has to be functionalized, the lithiation was performed either by a regioselective “direct” deprotonation (which

Figure 3. Bidentate ligands developed in this study.

involves the presence of ortho-directing groups such as a methoxy or a chloride group on the substrate; method A) or by a halogen metal exchange (for the brominated substrates; method B). Starting from complex 1, lithiation by nBuLi followed by electrophilic quenching with PPh2Cl under the same experimental conditions as those described for other electrophiles22 provided the two regioisomers 5a,b, which were isolated in a C2:C3 ratio of 70:30 (Table 1, entry 1). When complex 2 was reacted under identical conditions, only the regioisomer 6, substituted ortho to the methoxy group, was obtained23 (Table 1, entry 2). No C1 deprotonation was observed during the synthesis of 5 and 6, in good agreement with what was already known.22 To functionalize the terminal positions, we used bromosubstituted complexes as starting materials. The halogenmetal exchange in bromo complexes 3 and 4 was realized by following the procedure recently described.19 These conditions allowed us to introduce a phosphinyl group at the C2 carbon of 7 and at the 3531

dx.doi.org/10.1021/om200231p |Organometallics 2011, 30, 3530–3543

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Table 2. Two Consecutive LithiationElectrophilic Quenching Sequences Applied to Complex 2

entry 1

E1X Ph2(O)PCl

E1 P(O)Ph2

product

yield (%)

9

70

E2X

2 3 4

a

H2CdNMe2þI

CH2NMe2

10

77

E2

product

yield (%)

(CH2)2I2

I

11

37

Ph2PCl

PPh2

12

90%)

a Conditions: [substrate] = 0.39 mol L1, [nucleophile] = 1.16 mol L1, [Pd(η3-allyl)Cl]2 = 0.01 mol L1, [BSA] = 1.16 mol L1 b Time in minutes except when indicated. c Time in hours.

full conversion was reached within 10 min, as compared to hours in all other cases (Table 5). The same observation can be made in the case of both regioisomers 15 and 20 at 40 °C, where the C2substituted phosphorus ligand provides an almost 4 times faster reaction than the C3-substituted ligand (entries 5 and 6), supporting the idea that the influence of the η5 system on the phosphorus atom might depend on the position of this atom on the π system.38 It is suggested that the less basic the phosphorus atom, the faster the reaction. This is consistent with the increase of electrophilicity of the palladium center favoring most probably the nucleophilic addition to the allylic moiety. To find out more about the electronic density of the new phosphorus ligands, we used the method of Allen and Taylor,3941 who demonstrated that the 1JPSe coupling constant was a good measure of the phosphine basicity, irrespective of the size of the phosphine. Thus, the PSe complexes were readily prepared from the mono- and disubstituted ligands applied in catalysis, 5a and 68 (Table 5), in quantitative yields by heating a solution of the ligand with an excess of selenium in chloroform for 5 h. This procedure delivered the PSe derivatives, which are the first examples of such complexes ever described in the literature (Table 6). Table 6 contains a summary of the NMR data for the ligands investigated. The 764 Hz 1JSeP coupling constant value of complex 5a-Se is higher than those obtained for 6-Se and 8-Se at 743 and 741 Hz, in good agreement with the presence of an electron-donating methoxy group “ortho” or “para” to the phosphorus atom (entries 1, 2, and 4). A milder effect is observed when MeO is located at the “meta” position, with a J value of 756 Hz (entry 3). More interesting is the comparison of the coupling constants of 5a-Se and 6-Se, which have values of 764 and 743 Hz, respectively (entries 1 and 2), with those of the aryl-substituted phosphino ligands PPh3dSe and PPh2(2-OMe-C6H4) with J values of 728.9 and 720 Hz, respectively (entries 5 and 6). This underlines that when the phenyl group of the P atom is replaced by the (η5-cyclohexadienyl)Mn(CO)3 ligand, a strong π-acceptor effect is observed on the P atom and the Lewis acidity of the

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Table 6. 31P NMR Data (δ in ppm and J in Hz) for P(III) and P(V) Derivatives in CDCl3

catalyst is increased, which could explain the very fast reaction observed at 0 °C or room temperature with the corresponding catalysts (Table 5). These data suggest first that the Mn(CO)3 tripod coordinated in an η5 manner to the cycle amplifies the electronic effects of the substituents (here only electron donating) (764743 Hz is greater than 728.9720 Hz) and second that this metal coordination noticeably decreases the electron density at the phosphorus atom.42 We can also conclude that the Lewis acidity of the phosphorus atom decreases in the order 5a-Se > 7-Se > 6-Se > 8-Se > PPh3 > PPh2(2-OMe-C6H4). However, at this stage, it is difficult to link the efficiency of the catalyst only to the acidity of the phosphorus atom of the ligand, because the electron density at phosphorus is not the only parameter governing the rate of the process and the steric hindrance of the ligand probably plays a role. 2.4.1. Preparation of Enantioenriched Ligands. As the new metalloligands were effective in catalysis, we next investigated their preparation in enantiopure form in order to use them in enantioselective catalysis. Planar chiral ligands which only possess planar chirality are relatively rare.5,11,12,43 Very few syntheses of enantioenriched η5 Mn complexes have been described in the literature over the last 3 years. They involve either a resolution via a chiral nonracemic auxiliary or an enantioselective synthesis starting from enantiopure η6 Mn complexes, and these two methodologies were applied in the present study to the synthesis of enantioenriched Mn-based ligands. 2.4.1.1. Resolution via a Chiral Nonracemic Palladium Auxiliary. In the literature, enantioenriched η5 Mn complexes have been obtained by resolution of a planar chiral formyl-substituted η5 complex through the formation of the corresponding aminal from a chiral diamine.22a,c,44 We adopted an analogous method involving an enantiopure palladium auxiliary which could coordinate the PPh2 substituent of the racemic (η5-cyclohexadienyl)Mn(CO)3 complexes. The dimeric palladium complex (S)-(þ)-bis(μ-chloro)bis[2[(dimethylamino)ethyl]phenyl-C2,N]dipalladium(II) ((S)-35) was chosen as the chiral resolving agent.45 Following the protocol previously described by Mino and co-workers,45c (()-6 was totally converted to the diastereoisomeric palladium complex mixture 36, which was purified on a silica gel chromatography column thanks to a suitable degree of separation of the two diastereoisomers (Scheme 6). (S,3pS)-36 and (S,3pR)-3623,46 were isolated in 40% and 34% yields, respectively, with dr g 95:5. The diastereoisomeric purity of each fraction was unambiguously confirmed by 1 H NMR analysis: the signal corresponding to the H4 proton of each diastereoisomer, ortho to the chelating phosphine, resonates 3535


Organometallics at 5.91 and 6.52 ppm, respectively. The configuration of the planar chiral moiety was determined by single-crystal X-ray analysis of the more polar palladium complex (δ(H4) 5.91 ppm), which revealed the pS configuration for the phosphine complex (S,3pS)-3623 on the basis of the S configuration of the enantiopure phenethylamine moiety. Each diastereoisomer was then treated with ethylenediamine in order to release the enantiopure complexes (3pS)-6 and (3pR)-6 in 77% and 84% yields, respectively, and 90% ee. Using the same procedure, we then carried out further in vestigations to resolve 7 and 8. The reaction of the palladium complex (S)-35 with 7 and 8 readily proceeded to deliver the corresponding bimetallic derivatives 37 and 38 in 95 and 97% yields, respectively, as a mixture of two diastereomers (Scheme 7). Unfortunately, they could not be separated on a chromatography column. In any event, to our surprise, by slow diffusion of pentane in a dichloromethane solution of 38 mixture at low temperature two kinds of shiny crystals, with two very distinct colors, yellow and orange, appeared. They could be easily separated and isolated

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in 32 and 34% yields and with 88 and 86% de, respectively, as evidenced by 1H NMR spectra. The assignment of the pS configuration of the planar chiral moiety was determined by single-crystal X-ray analysis of one of the yellow crystals (Figure 6 and Table 3).26 The C1C6C5/ C1C2C3C4C5 dihedral angle has a slightly smaller value than that for 15, 33, and 34: 35.44(15)° in comparison with 41° (Table 3). The palladium atom is located at the side opposite the Mn(CO)3 tripod. The structure shows a square-planar coordination of the palladium, with the sum of all bond angles of 359.8°. Each diastereoisomer of 38, after treatment with ethylenediamine, delivered the enantioenriched (1pS)-8 and (1pR)-8 in 88% yield and with 88 and 86% ee, respectively. 2.4.1.2. Enantioselective Syntheses. The second procedure used for the preparation of Mn-based ligands in enantioenriched forms was based on enantioselective syntheses starting from enantiopure η6 Mn complexes. In 2009, we published the first method of resolution of cationic ortho- and meta-disubstituted (η6arene)tricarbonylmanganese complexes based on D-(þ)-camphor

Scheme 6. Resolution of Complex 6

Figure 6. ORTEP view of yellow (S,1pS)-38, with thermal ellipsoids at the 30% probability level. Selected bond lengths (Å): PdN1 = 2.134(2), PdP1 = 2.2611(7), PdC29 = 2.003(2), PdCl = 2.4099(7).

Scheme 7. Resolution of Complexes 7 and 8

3536


Organometallics Scheme 8. Enantioselective Synthesis of Bidentate PN Ligand 15

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Table 7. Enantioselective Catalysis Tests at 20 °C with Mono- and Bidentate Ligands Based on η5 Mn Complexes (Total Conversion and Yield >90%)a entry 1

2

3

4

5

6 ()-15

ligand

()-6

(þ)-6

()-8

(þ)-8

(þ)-15

timeb

7

7

15

15

5

5

eec

35 (R)

43 (S)

6 (R)

3 (S)

83 (S)

79 (R)

Conditions: [substrate] = 0.39 mol L1, [nucleophile] = 1.16 mol L1, [Pd(η3-allyl)Cl]2 = 0.01 mol L1, [BSA] = 1.16 mol L1. b Time in min. c In percent; determined by HPLC using a chiral Chiralpak AD-H column. Separation conditions: hexane/iPrOH 9/1, trR = 11.2 min, trS = 15.4 min. a

Figure 7. Enantioenriched mono- and bidentate ligands synthesized in the present study.

enolate addition, separation of the corresponding η5-cyclohexadienyl diastereoisomers, and then elimination of the chiral auxiliary by rearomatization.20,47 The addition of PhMgBr to the enantiomer 1pS of the cationic tricarbonylmanganese m-bromoanisole complex prepared according to this procedure20 delivered the corresponding enantiopure η5 complex (2pS)-3 with the same planar chirality, as it is well precedented that the nucleophile usually attacks exo to the Mn(CO)3 entity (Scheme 8). Halogen metal exchange followed by treatment with methanol gave the enantiopure (2pS)-2, a key organometallic chiral synthon that cannot be obtained through resolution of the (η6-anisole)Mn(CO)3 parent complex, because this latter monosubstituted complex has no planar chirality. The following steps are the same as in the racemic series, and two consecutive lithiationelectrophilic quenches with the Eschenmoser salt and then with PPh2Cl as electrophile delivered the enantiopure (2pR)-15 from (2pS)-10. As neither lithiation nor electrophilic quenching involves planar chirality, we assumed that this methodology does not modify the stereochemical information and compounds (2pS)-3, (2pS)-2, (2pS)-10, and (2pR)-15 were obtained in >98% ee. With the cationic 1pR enantiomer as the starting material, the same protocol led to (2pS)-15. 2.4.2. Asymmetric Catalysis. The potential of the enantiopure ligands 6, 8, and 15 (Figure 7) in asymmetric catalysis was then surveyed and tested in the allylic alkylation represented in Scheme 5.

Typically, the catalytic tests were performed at 20 °C, and the results (followed by 1H NMR spectroscopy, total conversion and yield >90%) are gathered in Table 7. Fair ee’s were obtained with ligands 6 (entries 1 and 2), and very low ee’s are observed with ligands 8 (entries 3 and 4); however, much better ee’s are achieved with (N,P) ligands 15, which performed more efficiently in this reaction. Thus, after 5 min the substitution products were formed in excellent yields with ee’s of 83 and 79% (entries 5 and 6). The use of lower temperatures did not give higher levels of induction. These results suggest a correlation between the coordination ability of the ligand and the selectivity of the corresponding catalysts. Indeed, the lowest selectivity is obtained with the monophosphine 8. Ligand 6, which possesses a methoxy group close to the phosphorus moiety, provides a catalyst showing moderate selectivity. The assistance of the methoxy group, through either steric hindrance or chelation, can be reasonably thought to support the observed variation of selectivity. Finally, the catalyst bearing the P,N bidentate ligand 15 exhibits the highest selectivity.

3. CONCLUSION We have reported the synthesis of phosphino-substituted (η5cyclohexadienyl)Mn(CO)3, potential mono- and bidentate ligands, in good to excellent yields by functionalization of the η5 scaffold using lithiationelectrophilic quenching sequences and palladiumcatalyzed coupling reactions. The coordination properties of one monodentate and one bidentate P,N η5 ligand were studied, and the corresponding bimetallic Mn/Pd complexes were isolated and structurally characterized by X-ray crystallography. The resolution of three of them, involving two different approaches by using either a chiral nonracemic palladium auxiliary or an enantioselective synthesis, allowed us to isolate the first examples of enantioenriched ligands based on a η5 Mn unit. The catalytic efficiency of a selection of ligands was evaluated in a model reaction (the palladium-catalyzed allylic substitution) which was revealed to be extremely fast and which occurred with excellent yields and total conversion in all the examples studied. The first results obtained in asymmetric catalysis, although not optimized, are satisfying and open a new area for the application of such η5 Mn complexes in this field. 4. EXPERIMENTAL SECTION 4.1. General Procedures. All reactions were routinely performed under a dry nitrogen atmosphere using standard Schlenk techniques. THF was dried over sodium benzophenone ketyl and distilled. N,N,N0 , 3537


Organometallics N0 -Tetramethylethylenediamine (TMEDA) was distilled over KOH and stored under nitrogen over 4 Å molecular sieves. Acetone and benzaldehyde were distilled over K2CO3. NMR spectra were recorded on a Bruker ARX 200 MHz or Avance 400 MHz spectrometer. Infrared spectra were measured on a Bruker Tensor 27 spectrometer. Elemental analyses were performed by the Service Central d’Analyse du CNRS. Mass spectra were performed for MALDI-TOF by the Plate-Forme Spectrometrie de Masse and Proteomique (IFR83, UPMC), for ES-MS by the Groupe de Spectrometrie de Masse (UMR 7613, UPMC), and for EI-MS by the Service de Spectrometrie de Masse de l’ENS (Chemistry Department, Paris). Complexes 1,48 2,48 3,19 4,19 21,18b 22,22c 23,22b and 2422b were synthesized according to procedures previously described in the literature.

4.2. Typical Procedure for LithiationElectrophilic Quenching Sequence: Method A. A solution of (η5-cyclohexadienyl)Mn(CO)3 (0.5 mmol) and freshly distilled TMEDA (02 equiv; see Table 1) in 5 mL of THF was cooled to 78 °C. A solution of n-BuLi (1.6 M in hexanes; 1.42 equiv; see Table 1) was slowly added. The mixture was stirred for 15 min to 2 h (see Table 1) at 78 °C before the addition of the electrophile (1.62.5 equiv; see Table 1). The mixture was stirred for another 1 h at 78 °C before it was warmed to room temperature and quenched by addition of H2O. After extraction of the mixture by Et2O, the combined organic layers were washed with a saturated aqueous NaCl solution and dried over MgSO4. After filtration and concentration in vacuo, the crude mixture was purified by flash chromatography on silica gel to afford the pure functionalized η5-cyclohexadienyl complex.

4.3. Typical Procedure for MetalHalogen Exchange and Then Electrophilic Quenching: Method B. n-BuLi (3 equiv) was

dropped into a THF solution cooled to 78 °C. Then a solution of the η5 bromo-substituted complex (1 equiv) in THF was very slowly added, giving rise to a deep yellow-orange solution that was stirred at 78 °C for 10 min. The electrophile (3.5 equiv) was added, and the solution was very slowly warmed to room temperature. The crude mixture was hydrolyzed with water, and the aqueous layer was extracted with diethyl ether. The organic layers were washed with water and then brine and dried over MgSO4. After filtration over Clarcel and evaporation of the solvents, the mixture was purified by flash chromatography on silica gel.

4.4. Typical Procedure for Palladium-Catalyzed Coupling: Method C. Pd2(dba)3 (0.03 mmol) and AsPh3 (0.11 mmol) were

successively added to the η5 complex (0.32 mmol) in 7 mL of anhydrous degassed DMF. After 5 min at room temperature tributylstannylthiophene (0.32 mmol) was introduced. The mixture was stirred for 23 h at room temperature, poured into 50 mL of ice-cold water, and extracted twice with 30 mL of pentane. The combined organic phases were washed with H2O (20 mL) and dried over MgSO4. After filtration and concentration in vacuo, the crude mixture was purified by flash chromatography on silica gel to afford the pure functionalized η5-cyclohexadienyl complex. 4.5. Typical Procedure for Catalysis. In a Schlenk tube were introduced [Pd(η3-allyl)Cl]2 (0.03 equiv) and the monodentate ligand (0.12 equiv.) in 1 mL of CH2Cl2, and the mixture was stirred for 30 min. In a second tube, KOAc (0.1 equiv), BSA (3 equiv) (KOAc and BSA generate in situ the nucleophile in order to keep the concentration of nucleophile constant with respect to the catalyst during the reaction) and dimethyl malonate (3 equiv) were introduced with 1 mL of CH2Cl2; the mixture was stirred for 30 min and added to the first Schlenk tube together with a solution of allyl acetate (1 equiv) in 1 mL of CH2Cl2. The time and reaction temperature are detailed in Tables 5 and 6. 5a,b (method A) could not be separated by a chromatography column, but the difference in their solubilities in pentane allowed us to isolate pure 5a (partially soluble in pentane) and a mixture of 5a and 5b.

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Data for 5a (30% yield) are as follows. 1H NMR (400 MHz, CDCl3): δ 3.44 (t, 3J = 6.3 Hz, 1H, H5), 3.60 (t, 3J = 6.3 Hz, 1H, H6), 3.98 (t, 3J = 6.3 Hz, 1H, H1), 5.14 (t, 3J = 6.3 Hz, 1H, H4), 5.30 (d, 3J = 2.9 Hz, 1H, H3), 6.92 (m, 4H, HAr), 7.02 (t, 3J = 6.9 Hz, 2H, HAr), 7.30 (m, 9H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 40.6 (d, 3JCP = 4 Hz, C6), 56.5 (C5), 60.4 (d, 2JCP = 26 Hz, C1), 82.5 (d, 2JCP = 6 Hz, C3), 96.7 (C4), 111.1 (d, 1JCP = 17 Hz, C2), 125.9 (CHAr), 126.9 (CHAr), 128.6 (d, 3 JCP = 7 Hz, CHAr), 128.8 (CHAr), 128.9 (d, 3JCP = 7 Hz, CHAr), 129.0 (CHAr), 130.2 (CHAr), 134.0 (d, 2JCP = 20 Hz, CHAr), 134.8 (d, 1JCP = 12 Hz, CAr), 222.7 (Mn(CO)3) ppm. 31P NMR (162 MHz, CDCl3): δ 2.7 (PPh2) ppm. IR (ATR Diamant): ν 1910 (Mn(CO)3), 2010 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 479.0616 (M þ Hþ), calcd for C27H21MnO3P 479.0609. Anal. Calcd: C, 67.79; H, 4.21. Found: C, 67.65; H, 4.12. Data for 5b (13% yield) are as follows. 1H NMR (400 MHz, CDCl3): δ 3.50 (m, 2H, H1 and H5), 3.82 (t, 3J = 6.0 Hz, 1H, H6), 4.79 (m, 2H, H2 and H4), 6.85 (m, 3H, HAr), 6.93 (m, 2H, HAr), 7.18 (m, 8H, HAr), 7.35 (t, 3J = 7.0 Hz, 2H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 38.5 (C6), 59.4 (d, 3JCP = 2.0 Hz, C1 and C5), 91.3 (C3), 100.9 (d, 2JCP = 18.1 Hz, C2 and C4), 125.5 (CHAr), 126.7 (CHAr), 128.4 (CHAr), 128.5 (CHAr), 128.6 (CHAr), 129.1 (CHAr), 133.8 (d, 2JCP = 19.5 Hz, CHAr), 136.4 (d, 1JCP = 9.7 Hz, CAr), 143.8 (C7) ppm. 31P NMR (162 MHz, CDCl3): δ 3.6 (PPh2) ppm. IR (ATR Diamant): ν 1927 (Mn(CO)3), 2021 (Mn(CO)3) cm1. Data for 6 (83% yield; method A) are as follows. 1H NMR (400 MHz, CDCl3): δ 3.35 (m, 1H, H5), 3.43 (s, 3H, OMe), 3.56 (m, 1H, H1), 4.02 (t, 3J = 6.0 Hz, 1H, H6), 4.39 (d, 3J = 7.4 Hz, 1H, H4), 6.98 (d, 3J = 7.0 Hz, 2H, HAr), 7.227.37 (m, 9H, HAr), 7.447.47 (m, 4H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 41.6 (C6), 42.3 (C1), 55.1 (OMe), 57.7 (C5), 81.2 (d, 1JCP = 20 Hz, C3), 95.7 (C4), 125.5 (CHAr), 127.0 (CHAr), 128.6 (d, 3JCP = 7 Hz, CHAr), 128.8 (CHAr), 128.9 (d, 3JCP = 7 Hz, CHAr), 128.9 (CHAr), 129.8 (CHAr), 133.4 (d, 2JCP = 20 Hz, CHAr), 135.0 (d, 1JCP = 12 Hz, CAr), 135.1 (d, 2JCP = 20 Hz, CHAr), 137.6 (d, 1JCP = 12 Hz, CAr), 146.2 (d, 2JCP = 14 Hz, C2), 147.7 (CAr) ppm. 31P NMR (162 MHz, CDCl3): δ 17.2 (PPh2) ppm. IR (ATR Diamant): ν 1917 (Mn(CO)3), 2009 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 509.0266 (M þ Hþ), calcd for C28H23MnO4P 509.0714. Anal. Calcd for C28H23MnO4P: C, 66.15; H, 4.36. Found: C, 66.06; H, 4.07. Data for 7 (96% yield; method B) are as follows. 1H NMR (200 MHz, CDCl3): δ 3,37 (d, 3J = 5.9 Hz, 1H, H5), 3.46 (d, 3J = 5.9 Hz, 1H, H1), 3.54 (s, 3H, OMe), 4.10 (t, 3J = 5.9 Hz, 1H, H6), 5.35 (s, 1H, H3), 6.866.90 (m, 2H, HAr), 7.007.09 (m, 4H, HAr), 7.197.49 (m, 9H, HAr) ppm. 13C NMR (400 MHz, CDCl3): δ 41.3 (C5), 43.0 (d, JCP = 4 Hz, C6), 54.6 (OMe), 60.4 (d, 1JCP = 26 Hz, C1), 71.3 (d, JCP = 8 Hz, C3), 107.2 (d, JCP = 17 Hz, C2), 125.7 (CHAr), 126.8 (CHAr), 128.6 (CHAr), 128.7 (CHAr), 128.8 (CHAr), 128.9 (CHAr), 129.0 (CHAr), 129.9 (CHAr), 133.0 (d, JCP = 18 Hz, CHAr), 133.9 (d, JCP = 20 Hz, CHAr), 135.1 (d, JCP = 20 Hz, CHAr), 143.3 (C4), 146.6 (CAr), 222.4 (Mn(CO)3) ppm. 31P NMR (162 MHz, CDCl3): δ 2.0 (PPh2) ppm. IR (ATR Diamant): ν 1902 (Mn(CO)3), 2013 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 509.0709 (M þ Hþ), calcd for C28H23MnO4P 509.0714. Data for 8 (67% yield; method B) are as follows. 1H NMR (200 MHz, CDCl3): δ 3,27 (dd, 3J = Hz, 4J = Hz, 1H, H5), 3.50 (s, 3H, OMe), 4.13 (t, 3J = Hz, 1H, H6), 4.87 (t, 3J = Hz, 1H, H2), 5.79 (dd, 3J = Hz, 4J = Hz, 1H, H3), 6.806.82 (m, 2H, HAr), 6.957.26 (m, 13H, HAr) ppm. 13C NMR (400 MHz, CDCl3): δ 41.7 (d, 3JCP = 9 Hz, C5), 48.4 (d, 2JCP = 24 Hz, C6), 54.8 (OMe), 68.6 (C3), 70.6 (d, 1JCP = 30 Hz, C1), 97.1 (d, 2JCP = 4 Hz, C2), 126.9 (CHAr), 127.5 (CHAr), 128.0 (d, 2JCP = 7 Hz, CHAr), 128.3 (CHAr), 128.5 (CHAr), 128.6 (CHAr), 129.7 (CHAr), 133.7 (d, 2 JCP = 20 Hz, CHAr), 135.0 (d, 2JCP = 20 Hz, CHAr), 135.5 (d, 1JCP = 12 Hz, CAr), 135.7 (d, 1JCP = 11 Hz, CAr), 143.1 (C4 or C7), 146.5 (C4 or C7) ppm. 31P NMR (162 MHz, CDCl3): δ 4.4 (PPh2) ppm. IR (ATR 3538


Organometallics Diamant): ν 1929 (Mn(CO)3), 2021 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 509.0709 (M þ Hþ), calcd for C28H23MnO4P 509.0714. Data for 923 (70% yield; method A) are as follows. 1H NMR (400 MHz, CDCl3): δ 3.14 (s, 3H, OMe), 3.42 (tapp, 3J = 6.0 Hz, 1H, H1), 3.63 (tapp, 3J = 6.0 Hz, 1H, H5), 4.02 (t, 3J = 6.0 Hz, 1H, H6), 5.74 (t, 3J = 7.0 Hz, 1H, H4), 6.97 (d, 3J = 7.0 Hz, 2H, H8), 7.227.29 (m, 5H, HAr), 7.427.56 (m, 4H, HAr), 7.757.89 (m, 4H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 41.5 (C6), 42.7 (C1), 54.3 (OMe), 60.3 (C5), 97.3 (C4), 125.5 (CHAr), 127.2 (CHAr), 127.9 (d, 2JCP = 12 Hz, CHAr), 128.6 (d, 2JCP = 12 Hz, CHAr), 128.7 (CHAr), 131.9 (CHAr), 132.1 (d, 3JCP = 10 Hz, CHAr), 132.8 (CHAr), 147.2 (C2), 216.6 (Mn(CO)3) ppm. 31P NMR (CDCl3): δ 30.3 ppm. IR (neat): ν 1952 (Mn(CO)3), 2015(Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 525.0658 (M þ Hþ), calcd for C28H23O5MnP 525.0664. Data for 1023 (77% yield; method A) are as follows. 1H NMR (400 MHz, CDCl3): δ 2.41 (s, 6H, NMe2), 3.06 (d, 2J = 12.5 Hz, 1H, H11), 3.31 (ddd, 3J = 7.3 Hz, 3J = 6.2 Hz, 4J = 1.6 Hz, 1H, H5), 3.40 (dd, 3J = 6.2 Hz, 4J = 1.6 Hz, 1H, H1), 3.42 (s, 3H, OMe), 3.91 (tapp, 3J = 6.2 Hz, 1H, H6), 4.21 (d, 2J = 12.5 Hz, 1H, H11), 5.05 (d, 3J = 7.3 Hz, 1H, H4), 6.94 (d, 3J = 7.3 Hz, 2H, HAr), 7.13 (t, 3J = 7.3 Hz, 1H, HAr), 7.21 (tapp, 3J = 7.3 Hz, 2H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 41.5 (C1), 42.6 (C6), 45.5 (NMe2), 54.8 (OMe), 56.2 (C5), 59.0 (C11), 85.3 (C3), 97.2 (C4), 125.6 (CHAr), 127.0 (CHAr), 128.8 (CHAr), 143.4 (C2 or CAr), 147.5 (C2 or CAr), 222.9 (Mn(CO)3) ppm. IR (neat): ν 1909 (Mn(CO)3), 2006 (Mn(CO)3) cm1. HRMS (MALDI TOF, positive mode): m/z 382.0798 (M þ Hþ), calcd for C19H21O4MnN 382.0851. Data for 11 (37% yield; method A) are as follows. 1H NMR (400 MHz, CDCl3): δ 2.81 (s, 3H, OMe), 3.50 (d, 3J = 5.9 Hz, 1H, H1), 3.88 (t, 3J = 5.9 Hz, 1H, H6), 4.31 (d, 3J = 5.9 Hz, 1H, H5), 6.98 (d, 3J = 7.0 Hz, 1H, HAr), 7.307.57 (m, 9H, HAr), 7.707.80 (m, 4H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 43.8 (C1), 44.0 (C6), 54.3 (OMe), 72.4 (C5), 76.8 (C3), 125.4134.4 (CHAr), 146.6 (C2), 149.4 (C4) ppm. 31P NMR (162 MHz, CDCl3): δ 35.0 (P(O)Ph2) ppm. IR (ATR Diamant): ν 1935 (Mn(CO)3), 2014 (Mn(CO)3) cm1. Anal. Calcd: C, 51.72; H, 3.26. Found: C, 51.36; H, 3.19. Data for 13 (95% yield; method A) are as follows. 1H NMR (200 MHz, CDCl3): δ 0.32 (s, 1H, SiMe3), 2.27 (s, 6H, NMe2), 3.38 (d, 3J = 5.3 Hz, 1H, H5), 3.47 (s, 3H, OMe), 3.59 (d, 3J = 4.9 Hz, 1H, H1), 3.67 (s, 2H, H11), 3.95 (m, 1H, H6), 7.10 (m, 5H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 0.4 (SiMe3), 41.9 (C1 or C6), 44.8 (NMe2), 54.7 (OMe), 54.9 (C11), 59.1 (C5), 91.3 (C3 or C4), 125.5 (CHAr), 126.5 (CHAr), 128.5 (CHAr), 143.0 (C2 or CAr), 148.3 (C2 or CAr), 222.9 (Mn(CO)3) ppm. IR (ATR Diamant): ν 1891 (Mn(CO)3), 1996 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 454.1241 (M þ Hþ), calcd for C22H29MnNO4Si 454.1246. Data for 1423 (94% yield; method A) are as follows. 1H NMR (400 MHz, CDCl3): δ 2.44 (s, 6H, NMe2), 3.39 (s, 3H, OMe), 3.49 (d, 3J = 6.1 Hz, 1H, H1), 3.59 (d, 2J = 12.8 Hz, 1H, H11), 3.84 (m, 2H, H5 and H6), 4.14 (d, 2J = 12.8 Hz, 1H, H11), 6.92 (d, 3J = 7.5 Hz, 2H, HAr), 7.15 (t, 3J = 7.3 Hz, 1H, HAr), 7.23 (t, 3J = 7.7 Hz, 2H, HAr). 13C NMR (100 MHz, CDCl3): δ 43.8 (C1), 45.5 (C6), 45.6 (NMe2), 55.3 (OMe), 60.7 (C11), 65.6 (C5), 78.9 (C3 or C4), 88.5 (C3 or C4), 125.6 (CHAr), 127.3 (CHAr), 128.9 (CHAr), 139.2 (CAr), 146.9 (C2). IR (neat): 1910 (Mn(CO)3), 2022 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 507.9812 (M þ Hþ), calcd for C19H20IMnNO4 507.9818. Data for 15 (84% yield; method A) are as follows. 1H NMR (400 MHz, CDCl3): δ 1.92 (s, 6H, NMe2), 3.19 (d, 3J = 6.1 Hz, 1H, H5), 3.28 (dd, 3J = 5.0 Hz, 4J = 1.3 Hz, 1H, H1), 3.61 (s, 3H, OMe), 3.83 (d, 2J = 12.7 Hz, 1H, H11), 3.97 (t, 3J = 6.0 Hz, 1H, H6), 4.14 (dd, 2J = 12.7 Hz, J = 4.1 Hz, 1H, H11), 6.81 (t, 3J = 7.6 Hz, 2H, HAr), 6.89 (t, 3J = 7.1 Hz, 2H, HAr), 6.95 (d, 3J = 7.2 Hz, 2H, HAr), 7.10 (t, 3J = 7.1 Hz, 1H, HAr), 7.207.37 (m, 8H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 37.7 (C1), 42.4 (C6), 43.9 (NMe2), 54.6 (d, 3JCP = 13.7 Hz, C11), 55.0 (OMe), 61.5

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(d, 2JCP = 5 Hz, C5), 91.3 (d, JCP = 21 Hz, C3 or C4), 109.5 (d, JCP = 23 Hz, C3 or C4), 125.6 (CHAr), 127.0 (CHAr), 127.7 (d, 3JCP = 8 Hz, CHAr), 127.9 (CHAr), 128.6 (d, 3JCP = 12 Hz, CHAr), 129.0 (CHAr), 129.5 (CHAr), 132.9 (d, 2JCP = 16 Hz, CHAr), 134.8 (CAr), 136.1 (d, 2JCP = 20 Hz, CAr), 143.6 (d, 3JCP = 5 Hz, C2), 147.1 (CAr), 222.4 (Mn(CO)3) ppm. 31P NMR (161 MHz, CDCl3): δ 9.2 (PPh2). IR (neat): ν 1925 (Mn(CO)3), 2010 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 566.1287 (M þ Hþ), calcd for C31H30O4MnNP 566.1293. Data for 16 (71% yield; method A) are as follows. 1H NMR (200 MHz, CDCl3): δ 2.55 (s, 6H, NMe2), 3.28 (d, 3J = 5.6 Hz, 1H, H5), 3.46 (d, 3J = 5.6 Hz, 1H, H1), 3.57 (s, 3H, OMe), 3.92 (m, 1H, H6), 3.98 (d, 2J = 12.8 Hz, 1H, H11), 4.17 (d, 2J = 12.8 Hz, 1H, H11), 7.13 (m, 10H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 41.4 (C5), 42.7 (C6), 45.7 (NMe2), 55.2 (OMe), 55.4 (C11), 57.5 (C1), 85.6 (C3), 115.8 (C4), 125.6 (CHAr), 126.9 (CHAr), 128.4 (CHAr), 128.7 (CHAr), 129.5 (CHAr), 133.3 (CAr), 133.5 (CHAr), 141.2 (CAr), 146.6 (C2), 222.1 (Mn(CO)3) ppm. IR (ATR Diamant): ν 1919 (Mn(CO)3), 2009 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 490.0879 (M þ Hþ), calcd for C25H25MnNO4S 490.0885. Data for 17 (obtained by NaBH4 reduction of the corresponding aldehyde: 80% yield (method A)) are as follows. 1H NMR (400 MHz, CDCl3): δ 2.33 (s, 6H, NMe2), 3.36 (m, 4H, OMe and H5), 3.55 (m, 2H, H1 and H11), 3.79 (d, 2J = 13.1 Hz, 1H, H12), 3.94 (m, 2H, H6 and H12), 4.71 (d, 2J = 10.3 Hz, 1H, H11), 7.07 (m, 2H, HAr), 7.22 (m, 3H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 41.5 (C6), 42.4 (C1), 44.5 (NMe2), 54.0 (C12), 55.1 (OMe), 58.2 (C5), 66.6 (C11), 85.3 (C4), 111.2 (C3), 125.4 (CHAr), 126.8 (CHAr), 128.8 (CHAr), 141.2 (C2 or C7), 147.8 (C2 or C7) ppm. IR (ATR Diamant): ν 1915 (Mn(CO)3), 2028 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 412.0956 (M þ Hþ), calcd for C20H23MnNO5 412.0957. Data for 18 (51% yield; method A) are as follows. 1H NMR (200 MHz, CDCl3): δ 2.10 (s, 6H, NMe2), 2.40 (s, 6H, NMe2), 2.68 (d, 2 J = 13.6 Hz, 1H, H11 or H12), 3.37 (m, 2H, H11), 3.44 (s, 3H, OMe), 3.63 (m, 2H, H11 and H13), 3.92 (m, 2H, H11 or H13 and H6), 6.94 (d, 3 J = 6.5 Hz, 1H, HAr), 7.12 (m, 3H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 41.3 (C1), 42.4 (C6), 45.8 (NMe2), 46.2 (NMe2), 54.1 (C11 or C13), 54.9 (OMe), 61.2 (C11 or C13), 86.6 (C3), 110.4 (C4), 125.8 (CHAr), 126.9 (CHAr), 128.7 (CHAr), 141.9 (C2 or CAr), 147.3 (C2 or CAr), 222.9 (Mn(CO)3) ppm. IR (ATR Diamant): ν 1916 (Mn(CO)3), 2005 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 439.1424 (M þ Hþ), calcd for C22H28MnN2O4 439.1430. Data for 19 (57% yield; method B) are as follows. 1H NMR (200 MHz, CDCl3): δ 2.15 (s, 6H, NMe2), 2.50 (d, 2J = 10.3 Hz, 1H, H11), 3.05 (d, 2J = 10.3 Hz, 1H, H11), 3.37 (d, 3J = 5.8 Hz, 1H, H1), 3.45 (d, 3J = 5.8 Hz, 1H, H5), 3.57 (s, 3H, OMe), 3.97 (t, 3J = 5.8 Hz, 1H, H6), 5.75 (s, 1H, H3), 6.95 (d, 3J = 7.3 Hz, 2H, HAr), 7.13 (d, 3J = 7.3 Hz, 1H, HAr), 7.21 (t, 3J = 7.3 Hz, 2H, HAr) ppm. 13C NMR (400 MHz, CDCl3): δ 43.4 (C1 and C6), 45.5 (NMe2), 54.7 (OMe), 61.5 (C5), 65.6 (C7), 70.4 (C3), 106.8 (C4), 125.8 (CHAr), 127.0 (CHAr), 128.7 (CHAr), 142.5 (C2 or C8), 147.4 (C2 or C8), 222.8 (Mn(CO)3) ppm. IR (ATR Diamant): ν 1908 (Mn(CO)3), 2005 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 382,0849 (M þ Hþ), calcd for C19H21MnNO4 382,0851. Data for 20 (51% yield; method A) are as follows. 1H NMR (400 MHz, CDCl3): δ 2.08 (s, 6H, NMe2), 2.39 (dd, 4J = 6.1 Hz, 2J = 12.5 Hz, 1H, H11), 3.02 (s, 3H, OMe), 3.29 (d, 3J = 5.9 Hz, 1H, H1), 3.79 (m, 1H, H5), 4.02 (t, 3J = 5.9 Hz, 1H, H6), 4.31 (dd, 2J = 12.7 Hz, 4J = 5.1 Hz, 1H, H11), 7.02 (m, 2H, HAr), 7.23 (m, 8H, HAr), 7.69 (d, 5H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 41.1 (C1), 41.8 (C6), 45.3 (NMe2), 53.8 (OMe), 64.1 (C11), 64.2 (d, 3JCP = 5 Hz, C5), 88.3 (d, JCP = 36 Hz, C3), 125.8 (CHAr), 127.1 (CHAr), 127.6 (CHAr), 127.7 (d, 3JCP = 5 Hz, CHAr), 128.8 (d, 3JCP = 5 Hz, CHAr), 128.6 (CHAr), 128.7 (CHAr), 132.5 (d, 2JCP = 23 Hz, CHAr), 135.6 (d, 2JCP = 23 Hz, CHAr), 139.7 (d, 2JCP = 12 Hz, C2 or C4), 144.9 (d, 2JCP = 4 Hz, C2 or C4), 147.5 (CAr) ppm. 31 P NMR (162 MHz, CDCl3): δ 12.3 (PPh2) ppm. IR (ATR Diamant): 3539


Organometallics ν 1903 (Mn(CO)3), 2013 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 566.1287 (M þ Hþ), calcd for C31H30MnNO4P 566.1293. Data for 25 (44% yield; method A) are as follows. 1H NMR (200 MHz, CDCl3): δ 2.29 (s, 6H, NMe2), 2.99 (d, 2J = 13.1 Hz, 1H, H13), 3.35 (d, 2J = 13.1 Hz, 1H, H13), 3.54 (s, 3H, OMe), 3.58 (d, 3J = 3.9 Hz, 1H, H5), 4.35 (d, 3J = 6.2 Hz, 1H, H6), 5.73 (s, 1H, H3), 7.057.07 (m, 2H, HAr), 7.207.27 (m, 3H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 45.1 (C5), 45.8 (NMe2), 53.7 (C6), 55.1 (OMe), 62.0 (C13), 68.0 (C3), 81.1 (C1), 104.6 (C2), 126.4 (CHAr), 127.8 (CHAr), 128.7 (CHAr), 141.3 (C4 or C7), 143.9 (C4 or C7), 221.7 (Mn(CO)3) ppm. IR (ATR Diamant): ν 1926 (Mn(CO)3), 2021 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 416.0456 (M þ Hþ), calcd for C19H20O4ClNMn 416.0461. Data for 27 (85% yield; method C) are as follows. 1H NMR (200 MHz, CDCl3): δ 3.58 (s, 3H, OMe), 3.64 (dd, 3J = 6.3 Hz, 4J = 2.6 Hz, 1H, H5), 4.38 (d, 3J = 6.3 Hz, 1H, H6), 6.16 (d, 4J = 2.6 Hz, 1H, H3), 6.71 (d, 3J = 3.6 Hz, 1H, HAr), 6.806.87 (m, 3H, HAr), 7.207.26 (m, 4H, HAr), 9.84 (s, 1H, CHO) ppm. 13C NMR (100 MHz, CDCl3): δ 44.8 (C5), 50.7 (C6), 55.2 (OMe), 62.4 (C3), 72.2 (C1), 97.6 (C2), 126.5 (CHAr), 127.3 (CHAr), 127.4 (CHAr), 128.0 (CHAr), 129.0 (CHAr), 129.9 (CHAr), 140.4, 141.2, 145.5 (Cquat), 194.1 (CHO), 221.3 (Mn(CO)3) ppm. IR (ATR Diamant): ν 1724 (CHO), 1906 (Mn(CO)3), 2008 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 456.9916 (M þ Hþ), calcd for C21H15MnNaO5S 456.9918. Data for 28 (50% yield; method C) are as follows. 1H NMR (400 MHz, CDCl3): δ 2.65 (s, 1H, OH), 3.48 (s, 4H, OMe and H5), 4.03 (d, 3 J = 6.1 Hz, 1H, H6), 5.32 (m, 2H, H3 and HAr), 6.62 (t, 3J = 4.2 Hz, 1H, HAr), 6.83 (d, 3J = 3.1 Hz, 4H, HAr), 7.03 (d, 3J = 7.4 Hz, 4H, HAr), 7.31 (m, 2H, HAr), 7.78 (m, 2H HAr), 7.59 (t, 3J = 7.4 Hz, 4H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 43.3 (C5), 53.5 (C6), 54.7 (OMe), 61.5 (CAr), 73.4 (C3), 77.0 (CAr), 81.1 (CAr), 127.3 (CHAr), 127.4 (CHAr), 127.4 (CHAr), 127.7 (CHAr), 127.8 (CHAr), 127.9 (CHAr), 128.3 (CHAr), 128.6 (CHAr), 128.9 (CHAr), 130.3 (CHAr), 130.4 (CHAr), 131.1 (CHAr), 132.7 (CHAr), 137.9 (CAr), 139.8 (CAr), 142.4 (CAr), 142.5 (CAr), 143.4 (CAr), 148.3 (CAr) ppm. IR (ATR Diamant): ν 1926 (Mn(CO)3), 2013 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 611.0750 (M þ Hþ), calcd for C33H25MnNaO5S 611.0701. Data for 29 (89% yield; method C) are as follows. 1H NMR (400 MHz, CDCl3): δ 3.33 (s, 3H, OMe), 5.54 (dd, 3J = 6.3 Hz, 4J = 2.3 Hz, 1H, H5), 4.34 (d, 3J = 6.3 Hz, 1H, H6),5.41 (d, 4J = 2.3 Hz, 1H, H3), 6.77 (d, 3J = 2.4 Hz, 1H, HAr), 6.84 (t, 3J = 5.1 Hz, 2H, HAr), 6.96 (dd, 3J = 7.6 Hz, 4J = 2.4 Hz, 2H, HAr),7.20 (m, 3H, HAr), 7.44 (m, 3H, HAr), 7.64 (dd, 3J = 5.4 Hz, 4J = 2.0 Hz, 2H, HAr). 13C NMR (100 MHz, CDCl3): δ 44.7 (C5), 51.4 (C6), 54.7 (OMe), 64.9 (C1), 67.6 (C3), 103.6 (C2 or C17), 104.8 (C2 or C17), 125.9 (CHAr), 126.7 (CHAr), 127.5 (CHAr), 128.5 (CHAr), 128.8 (CHAr), 130.0 (CHAr), 135.9 (CHAr), 140.1 142.8, 146.0 (CAr). IR (ATR Diamant): ν 1919 (Mn(CO)3), 2016 (Mn(CO)3) cm1. Anal. Calcd: C, 60.71; H, 3.72. Found: C, 60.84; H, 3.89. Data for 30 (83% yield; method C) are as follows. 1H NMR (200 MHz, CDCl3): δ 2.31 (s, 6H, NMe2), 3.02 (d, 2J = 13.1 Hz, 1H, H13a), 3.27 (d, 2J = 13.1 Hz, 1H, H13b), 3.54 (s, 3H, OMe), 3.61 (dd, 3J = 6.2 Hz, 4J = 2.3 Hz, 1H, H5), 4.27 (d, 3J = 6.2 Hz, 1H, H6), 5.90 (d, 4J = 2.3 Hz, 1H, H3), 6.74 (d, 3J = 3.5 Hz, 1H, HAr), 6.846.87 (m, 1H, HAr), 7.117.30 (m, 6H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 44.7 (C5), 46.3 (NMe2), 51.2 (C6), 54.8 (OMe), 62.5 (C13), 69.2 (C1), 69.6 (C3), 108.3 (C2), 125.3 (CHAr), 126.7 (CHAr), 126.9 (CHAr), 127.5(CHAr), 128.4 (CHAr), 128.7 (CHAr), 141.3, 143.9 (CAr) ppm. IR (ATR Diamant): ν 1918 (Mn(CO)3), 2002 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 464.0722 (M þ Hþ), calcd for C23H23O4NMnS 464.0722. Data for 31 (89% yield; method C) are as follows. 1H NMR (200 MHz, CDCl3): δ 3.43 (s, 3H, OMe), 3.50 (dd, 3J = 6.1 Hz, 4J = 2.5 Hz, 1H, H5), 4.17 (d, 3J = 5.1 Hz, H6), 5.15 (d, 4J = 2.5 Hz, 1H, H3), 5.85 (d, 3J = 3.5 Hz, 1H, HAr), 6.60 (dd, 3J = 5.1 Hz, 4J = 3.5 Hz, 1H, HAr),

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6.97 (m, 4H, HAr), 6.99 (m, 2H, HAr), 7.08 (m, 3H, HAr), 7.25 (m, 2H, HAr), 7.48 (m, 5H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 43.4 (C5), 51.5 (C6), 54.7 (OMe), 70.3 (C3), 71.7 (d, 2JCP = 24 Hz, C1), 110.8 (d, 1JCP = 40 Hz, C2), 125.8 (CHAr), 126.7 (CHAr), 127.8 (CHAr), 127.9 (CHAr), 128.3 (d, 2JCP = 8 Hz, CHAr), 128.4 (CHAr), 129.0 (d, 2 JCP = 7 Hz, CHAr), 129.2 (CHAr), 130.1 (d, 3JCP = 3 Hz, CHAr), 134.3 (d, 2JCP = 21 Hz, CHAr), 134.7 (CAr), 135.6 (d, 2JCP = 20 Hz, CHAr), 136.5 (d, 1JCP = 8 Hz, CAr), 141.8 (CAr), 142.1 (d, 1JCP = 5 Hz, CAr), 144.8 (CAr) ppm. 31P NMR (162 MHz, CDCl3): δ 6.5 (PPh2) ppm. IR (ATR Diamant): ν 1925 (Mn(CO)3), 2010 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 591.0586 (M þ Hþ), calcd for C32H25O4MnPS 591.0585. 4.6. Synthesis of 32.23 The dimeric complex [(allyl)PdCl]2 (0.068 g, 0.20 mmol, 1 equiv) was introduced in a Schlenk tube. Then, under N2, complex 6 (0.213 g, 0.42 mmol, 2.1 equiv) was added. At 78 °C, Et2O (5 mL) was added and the mixture was stirred for 30 min at 78 °C before it was slowly warmed to room temperature. After concentration in vacuo, the crude mixture was washed with pentane and filtered. The palladium complex 32 was isolated in 63% yield as a cream-colored powder. Data for 32 (63% yield) are as follows. 1H NMR (400 MHz, CDCl3): δ 2.78 (d, J = 12.1 Hz, 1H, allyl), 3.02 (s, 3H, OMe), 3.05 (m, 1H), 3.07 (s, 3H, OMe), 3.16 (m, 1H), 3.35 (m, 1H), 3.47 (m, 2H), 3.563.76 (m, 4H), 4.01 (m, 2H), 4.72 (m, 2H), 5.56 (m, 2H), 6.06 (m, 1H), 6.24 (m, 1H), 7.007.06 (m, 4H, HAr), 7.207.43 (m, 18H, HAr), 7.657.77 (m, 8H, HAr) ppm. 31P NMR (161 MHz, CDCl3): δ 24.6, 25.4 ppm. IR (neat): 1926 (Mn(CO)3), 2015 (Mn(CO)3). HRMS (MALDI TOF, positive mode): m/z 655.0125 (M Cl), calcd for C31H27MnO4PPd 655.0062. 4.7. Synthesis of 33 and 34. The dimeric complex [(allyl)PdCl]2 (0.018 g, 0.05 mmol, 0.5 equiv) was introduced in a Schlenk tube. Then, under N2, complex 15 (0.055 g, 0.09 mmol, 1 equiv) was added. After addition of THF, the solution was stirred for 3 h at 40 °C and then cooled to room temperature. AgPF6 (0.023 g, 0.09 mmol, 1 equiv) was added. The mixture was stirred for 15 min and filtered. After concentration in vacuo, the yellow solid was isolated in 77% yield (0.029 g, 0.038 mmol). Data for 33 (77% yield) are as follows. 1H NMR (400 MHz, THF-d8; tentative assignments due to low resolution): δ 3.15 (m, 6H, H1 þ H5 þ 2H8 þ 2Hallyl), 3.53 (m, 5H, OMe þ 2Hallyl), 3.95 (m, 1H, H6), 6.06 (m, 1H, allyl), 7.007.5 (m, 15H, PPh2 þ Ph) ppm. 31P NMR (161 MHz, CDCl3): δ 32.0 (PPh2) ppm. IR (neat): 1934 (Mn(CO)3), 2016 (Mn(CO)3) cm1. Anal. Calcd: C, 54.56; H, 4.58. Found: C, 54.71; H, 4.73. 34 was prepared using the same experimental conditions as for 33, but THF was replaced by CH2Cl2. Data for 34 (64% yield) are as follows. 1H NMR (400 MHz, CD2Cl2; tentative assignments due to low resolution): δ 3.25 (m, 6H, H1 þ H5 þ 2H8 þ 2Hallyl), 3.64 (s, 3H, OMe), 3.85 (m, 2H, Hallyl), 4.04 (m, 1H, H6), 6.00 (m, 1H, Hallyl), 7.007.5 (m, 15H, HPPh2 þ HPh) ppm. 31P NMR (161 MHz, CDCl3): δ 31.1 (PPh2), 142.9 (PF6) ppm. Anal. Calcd: C, 47.60; H, 3.99. Found: C, 47.81; H, 4.14.

4.8. Resolution Procedure for Racemic Complexes (()-6, (()-7, and (()-8: Synthesis and Separation of Diastereoisomeric Complexes 36,23 37, and 38. A mixture of the racemic complex (0.4 mmol) and (S)-(þ)-bis(μ-chloro)bis[2-[(dimethylamino)ethyl]phenyl-C2,N]dipalladium(II) (0.2 mmol, 0.5 equiv) in toluene (3 mL) was stirred at room temperature for 1 h. After concentration in vacuo, the crude mixture was purified by flash chromatography on silica gel to separate the diastereoisomeric mixture. In the case of 37, attempts to separate the two diastereoisomers were unsuccessful. Data for (S,3pR)-36 (34% yield) are as follows. de: 90%. Rf = 0.66 (Et2O). [R]D20 = þ45 cm3 g1 dm1 (c 0.23 g/100 mL, CHCl3). 1H NMR (CDCl3): δ 1.84 (d, 3J = 6.6 Hz, 3H, H26), 2.69 (s, 3H, NMe), 2.76 (s, 3H, NMe), 2.89 (s, 3H, OMe), 3.36 (d, 3J = 6.4 Hz, 1H, H1), 3.47 3540


Organometallics (t, 3J = 7.1 Hz, 1H, H5), 3.75 (t, 3J = 5.7 Hz, 1H, H25), 3.95 (t, 3J = 5.9 Hz, 1H, H6), 6.396.46 (m, 2H, HAr), 6.52 (t, 3J = 7.8 Hz, 1H, H4), 6.84 (t, 3 J = 7.6 Hz, 1H, HAr), 6.93 (d, 3J = 7.0 Hz, 1H, HAr), 7.157.43 (m, 11H, HAr), 7.65 (dd, 3J = 7.4 Hz, 3J = 12.0, 2H, HAr), 7.80 (dd, 3J = 7.3 Hz, 3 J = 11.9 Hz, 2H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 21.7 (C26), 41.5 (C6), 43.1 (C1), 46.9 (NMe), 50.6 (NMe), 54.0 (OMe), 57.9 (d, 3 JCP = 10 Hz, C5), 76.0 (C25), 80.1 (d, 1JCP = 47 Hz, C3), 105.3 (d, 2JCP = 22 Hz, C4), 122.4 (CHAr), 124.2 (CHAr), 125.4 (d, 3JCP = 5 Hz, CHAr), 126.4 (CHAr), 126.9 (d, 2JCP = 12 Hz, CHAr), 127.2 (CHAr), 128.3 (d, 2 JCP = 11 Hz, CHAr), 128.9 (CHAr), 130.3 (d, 3JCP = 8 Hz, CHAr), 133.4 (d, 2JCP = 11 Hz, CHAr), 134.0 (CAr), 134.5 (CAr), 136.2 (d, 2JCP = 11 Hz, CHAr), 137.6 (d, 3JCP = 8 Hz, CHAr), 144.9 (C2), 147.1 (CAr), 152.9 (CAr), 154.6 (CAr) ppm. 31P NMR (161 MHz, CDCl3): δ 39.0 (PPh2) ppm. IR (neat): 1925 (Mn(CO)3), 2014 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 798.0568 (M þ Hþ), calcd for C38H37O4ClMnNPPd 798.0564. Data for (S,3pS)-36 (40% yield) are as follows. de: 90%. Rf = 0.50 (Et2O). [R]D20 = 50 cm3 g1dm1 (c 0.21 g/100 mL1, CHCl3). 1H NMR (400 MHz, CDCl3): δ 1.79 (d, 3J = 6.4 Hz, 3H, H26), 2.72 (s, 6H, NMe2), 2.99 (s, 3H, OMe), 3.29 (tapp, 3J = 6.5 Hz, H5), 3.37 (d, 3J = 5.9 Hz, 1H, H1), 3.79 (t, 3J = 5.8 Hz, 1H, H25), 3.93 (t, 3J = 6.0 Hz, 1H, H6), 5.91 (t, 3J = 7.8 Hz, 1H, H4), 6.46 (t, 3J = 7.2 Hz, 1H, HAr), 6.59 (t, 3 J = 6.8 Hz, 1H, HAr), 6.84 (t, 3J = 7.2 Hz, 1H, HAr), 6.93 (d, 3J = 6.8 Hz, 1H, HAr), 7.08 (d, 3J = 7.2 Hz, 2H, HAr), 7.227.27 (m, 4H, HAr), 7.327.37 (m, 4H, HAr), 7.44 (d, 3J = 6.8 Hz, 1H, HAr), 7.72 (dd, 3J = 7.0 Hz, 3J = 11.9 Hz, 2H, HAr), 7.95 (dd, 3J = 7.4 Hz, 3J = 11.5 Hz, 2H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 21.1 (C26), 40.9 (C6), 41.9 (C1), 46.6 (NMe), 50.4 (NMe), 54.0 (OMe), 58.0 (d, 3JCP = 10.3 Hz, C5), 75.7 (C25), 78.6 (d, 1JCP = 46 Hz, C3), 103.6 (d, 2JCP = 10.3 Hz, C4), 122.6 (CHAr), 124.3 (CHAr), 125.7 (d, 3JCP = 5.1 Hz, CHAr), 125.9 (CHAr), 126.8 (d, 2JCP = 12 Hz, CHAr), 127.2 (CHAr), 128.4 (d, 2JCP = 10.3 Hz, CHAr), 128.7 (CHAr), 128.9 (d, 3JCP = 5.1 Hz, CHAr), 129.9 (d, 3 JCP = 2.6 Hz, CHAr), 130.4 (d, 3JCP = 2.6 Hz, CHAr), 134.2 (d, 2JCP = 12 Hz, CHAr), 135.8 (d, 2JCP = 12 Hz, CHAr), 137.0 (d, 2JCP = 10.3, CHAr), 145.5 (C2), 147.2 (CAr), 151.7 (CAr), 154.4 (CAr) ppm. 31P NMR (161 MHz, CDCl3): δ 39.0 (PPh2) ppm. IR (neat): 1920 (Mn(CO)3), 2011 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 798.0596 (M þ Hþ), calcd for C38H37O4ClMnNPPd 798.0564. Data for 37 (95% yield) are as follows. Mixture of diastereoisomers. 1 H NMR (400 MHz, CDCl3): δ (d, 3J = 7.3 Hz, 6H, Me), 1.78 (d, 3 J = 6.5 Hz, 3H, NMe), 2.34 (m, 2H, H1 or H5), 2.57 (m, 2H, H1 or H5), 2.61 (d, 3J = 6.5 Hz, 3H, NMe), 2.76 (s, 6H, OMe), 3.77 (m, 2H, H25), 6.45 (m, 4H, H3 and HAr), 6.82 (m, 2H, HAr), 6.92 (m, 2H, HAr), 7.35 (m, 24H, HAr), 7.72 (m, 4H, HAr), 7.87 (m, 4H, HAr) ppm. IR (ATR Diamant): ν 1941 (Mn(CO)3), 2017 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 762.0812 (M Clþ), calcd for C38H36MnNO4PPd 762.0797. Data for (S,1pR)-38 (34% yield) are as follows. Orange crystals. de: 86%. [R]D20 = 103 cm3 g1 dm1 (c 0.8 g/100 mL, CHCl3). 1H NMR (400 MHz, CDCl3): δ 1.47 (d, 3J = 6.6 Hz, 3H, Me), 2.42 (d, J = 2.4 Hz, 3H, NMe), 2.83 (d, J = 2.4 Hz, 3H, NMe), 3.29 (m, 1H, H5), 3.41 (s, 3H, OMe), 4.07 (m, 1H, H31), 3.79 (t, 3J = 5.8 Hz, 1H, H25), 5.83 (m, 3H, H6 and HAr), 6.13 (t, 3J = 7.2 Hz, 1H, H3), 6.67 (m, 2H, H2 and HAr), 7.01 (d, 3J = 5.5 Hz, 2H, HAr), 7.08 (m, 5H, HAr), 7.27 (m 1H, HAr), 7.34 (t, 3J = 13.7 Hz, 2H, HAr), 7.42 (d, 3J = 5.9 Hz, 1H, HAr), 7.50 (dd, 3J = 7.6 Hz, 3J = 11.3 Hz, 2H, HAr), 8.13 (dd, 3J = 7.6 Hz, 3J = 11.3 Hz, 2H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 13.8 (C32), 42.8 (NMe), 45.2 (d, 3JCP = 10 Hz, C5), 45.2 (d, 2JCP = 7.3 Hz, C6), 48.8 (NMe), 54.8 (OMe), 67.3 (d, 3JCP = 10.0 Hz, C3), 71.4 (d, 1 JCP = 31.5 Hz, C1), 73.7 (C31), 101.8 (d, 2JCP = 9.2 Hz, C2), 122.5 (CHAr), 123.4 (CHAr), 125.2 (d, 3JCP = 5.5 Hz, CHAr), 126.9 (CAr), 127.3 (CHAr), 127.6 (CHAr), 127.7 (d, 2JCP = 10.5 Hz, CHAr), 128.3 (CHAr), 128.4 (CHAr), 128.5 (CHAr), 129.0 (CAr), 130.6 (CHAr), 131.6 (CHAr), 135.5 (d, 2JCP = 11.7 Hz, CHAr), 137.7 (d, 2JCP = 13.9 Hz, CHAr), 142.6

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(C4 or CAr), 146.6 (C4 or CAr), 151.9 (CAr), 154.8 (CAr) ppm. 31P NMR (162 MHz, CDCl3): δ 45.0 (PPh2) ppm. IR (ATR Diamant): ν 1909 (Mn(CO)3), 2013 (Mn(CO)3) cm1. HRMS (ESI, positive mode): m/z 624.1642 ([M Mn(CO)3 Cl þ Hþ], calcd for C35H37NOPPd 624.1648. Data for (S,1pS)-38 (32% yield) are as follows. Yellow crystals. de: 88%. [R]D20 = 140 cm3 g1 dm1 (c 0.6 g/100 mL, CHCl3). 1H NMR (400 MHz, CDCl3): δ 1.63 (d, 3J = 6.7 Hz, 3H, Me), 2.62 (s, 3H, NMe), 2.69 (s, 3H, NMe), 3.23 (m, 1H, H5), 3.34 (s, 3H, OMe), 5.79 (m, 2H, H6 and H25), 6.08 (t, 3J = 7.0 Hz, 1H, H3), 6.60 (d, 3J = 5.8 Hz, 1H, H2), 6.75 (m, 1H, HAr), 7.15 (m, 9H, HAr), 7.25 (m, 2H, HAr), 7.55 (m, 5H, HAr), 8.39 (m, 2H, HAr) ppm. 31P NMR (162 MHz, CDCl3): δ 43.9 (PPh2). IR (ATR Diamant): ν 1914 (Mn(CO)3), 2020 (Mn(CO)3). HRMS (ESI, positive mode): m/z 624.1642 [M Mn(CO)3 Cl þ Hþ], calcd for C35H37NOPPd 624.1648. 4.9. Decomplexation of (S,3pS)-36 and (S,3pR)-36. To one of the diastereoisomers (S,3pS)-36 and (S,3pR)-36 (0.1 mmol) was added a 0.1 M solution of ethylenediamine in chloroform (2 mL, 0.2 mmol) at room temperature, and the mixture was stirred for 10 min. After concentration in vacuo, the crude mixture was purified by flash chromatography on silica gel to afford (3pS)-6 and (3pR)-6 in 77 and 84% yields, respectively, with 90% ee. Under the same experimental conditions, the enantioenriched (1pS)-8 and (1pR)-8 were isolated in 88% yield and with 88 and 86% ee starting from (S,1pS)-38 and (S,1pR)38. (3pS)-6 (77% yield): [R]D20 = þ57 cm3 g1 dm1 (c 0.21 g/100 mL, CHCl3). (3pR)-6 (84% yield): [R]D20 = 58 cm3 g1 dm1 (c 0.21 g/100 mL, CHCl3). (1pS)-8 (88% yield): [R]D20 = 5.9 cm3 g1 dm1 (c 0.44 g/100 mL, CHCl3). (1pR)-8 (88% yield): [R]D20 = þ7.2 cm3 g1 dm1 (c 0.4 g/100 mL, CHCl3). (2pS)-3 (77% yield): [R]D20 = 1.5 cm3 g1 dm1 (c 0.20 g/100 mL, CHCl3). (3pR)-3 (65% yield): [R]D20 = þ1.5 cm3 g1 dm1 (c 0.17 g/100 mL, CHCl3). (2pS)-2 (96% yield): [R]D20 = 8.8 cm3 g1 dm1 (c 0.84 g/100 mL, CHCl3). (2pR)-2 (96% yield): [R]D20 = þ10.2 cm3 g1 dm1 (c 1.14 g/100 mL, CHCl3). (1pS)-10 (73% yield): [R]D20 = þ74.9 cm3 g1 dm1 (c 0.94 g/100 mL, CHCl3). (2pR)-10 (73% yield): [R]D20 = 59 cm3 g1 dm1 (c 0.88 g/100 mL, CHCl3). (2pS)-15 (84% yield): [R]D20 = þ271 cm3 g1 dm1 (c 0.80 g/100 mL, CHCl3). (2pR)-15 (84% yield): [R]D20 = 259 cm3 g1 dm1 (c 1.16 g/100 mL, CHCl3).

’ ASSOCIATED CONTENT Supporting Information. CIF files giving crystallographic data for complexes 15, 33, 34, and 38 and a table giving crystal data and refinement details for 15. This material is available free of charge via the Internet at http://pubs.acs. org.

bS

’ AUTHOR INFORMATION Corresponding Author

*E-mail: [email protected] (F.R.-M.); [email protected] (E.R.). 3541


Organometallics

’ ACKNOWLEDGMENT We thank Dr. J.-P. Tranchier (IPCM, UMR 7201, Universite P. and M. Curie, Paris) for helpful discussions, C. Meliet (USTL, ENSCL, UMR 8181, Villeneuve d’Ascq) for NMR studies, and the Ministere de l’Education Nationale and de la Recherche for a MENRT grant to D.C. ’ REFERENCES (1) (a) See for example: Arrayas, R. G.; Adrio, J.; Carretero, J. C. Angew. Chem., Int. Ed. 2006, 45, 7674. (b) Delacroix, O.; Gladysz, J. A. Chem. Commun. 2003, 665. (2) Jones, G. B.; Chapman, B. J.; Mathews, J. E. J. Org. Chem. 1998, 63, 2928. (3) Gibson, S. E.; Ibrahim, H. I. Chem. Commun. 2002, 2465. (4) Salzer, A. Coord. Chem. Rev. 2003, 242, 59. (5) Mu~niz, K. In Transition Metal Arene π-Complexes in Organic Synthesis and Catalysis; K€undig, E. P., Ed.; Springer-Verlag: Heidelberg, Germany, 2004; Topics in Organometallic Chemistry 7, pp 205233. (6) Bolm, C.; Xiao, L.; Hintermann, L.; Focken, T.; Raabe, G. Organometallics 2004, 23, 2362. (7) Bolm, C.; Kesselgruber, M.; Hermanns, N.; Hindelbrand, J. P.; Raabe, G. Angew. Chem., Int. Ed. 2001, 40, 1488. (8) Bolm, C.; Xiao, L.; Kesselgruber, M. Org. Biomol. Chem. 2003, 1, 145. (9) Okamoto, K.; Kimachi, T.; Ibuka, T.; Takemoto, Y. Tetrahedron: Asymmetry 2001, 12, 463. (10) Kudis, S.; Helmchen, G. Angew. Chem., Int. Ed. 1998, 37, 3047. (11) Son, S. U.; Park, K. H.; Lee, S. J.; Chung, Y. K.; Sweigart, D. A. Chem. Commun. 2001, 1290. (12) Lee, J. H.; Son, S. U.; Chung, Y. K. Tetrahedron: Asymmetry 2003, 14, 2109. (13) Deschamps, B.; Ricard, L.; Mathey, F. J. Organomet. Chem. 2004, 689, 4647. (14) Wechsler, D.; Rankin, M. A.; McDonald, R.; Ferguson, M. J.; Schatte, G.; Stradiotto, M. Organometallics 2007, 26, 6418. (15) see for example:Balssa, F.; Gagliardini, V.; Le Corre-Susanne, C.; Rose-Munch, F.; Rose, E.; Vaisserman, J. Bull. Soc. Chim. Fr. 1997, 134, 537. (16) (a) Boutonnet, J. C.; Levisalles, J.; Rose, E.; Precigoux, G.; Courseille, C.; Platzer, N. J. Organomet. Chem. 1983, 255, 317. (b) Boutonnet, J. C.; Rose-Munch, F.; Rose, E.; Jeannin, Y.; Robert, Y. J. Organomet. Chem. 1985, 297, 185. (c) Rose-Munch, F.; Rose, E.; Semra, A. J. Chem. Soc., Chem. Commun. 1986, 1551. (d) RoseMunch, F.; Rose, E. J. Chem. Soc., Chem. Commun. 1987, 942. (e) Djukic, J. P.; Rose-Munch, F.; Rose, E.; Dromzee, Y. J. Am. Chem. Soc. 1993, 115, 6434. (f) Djukic, J. P.; Rose-Munch, F.; Rose, E. Organometallics 1995, 14, 2027. (g) Balssa, F.; Gagliardini, V.; Rose-Munch, F.; Rose, E. Organometallics 1996, 15, 4373. (17) Comte, V.; Tranchier, J. P.; Rose-Munch, F.; Rose, E.; Perrey, D.; Richard, P.; Moise, C. Eur. J. Inorg. Chem. 2003, 1893. (18) (a) Auffrant, A.; Prim, D.; Rose-Munch, F.; Rose, E.; Vaissermann, J. Organometallics 2002, 21, 3500. (b) Auffrant, A.; Prim, D.; Rose-Munch, F.; Rose, E.; Schouteeten, S.; Vaissermann, J. Organometallics 2003, 22, 1898. (19) Eloi, A.; Rose-Munch, F.; Rose, E.; Lennartz, P. Organometallics 2009, 28, 5757. (20) Eloi, A.; Rose-Munch, F.; Rose, E.; Pille, A.; Lesot, P.; Herson, P. Organometallics 2010, 29, 3876. (21) Prim, D.; Andrioletti, B.; Rose-Munch, F.; Rose, E.; Couty, F. Tetrahedron 2004, 60, 3325. (22) (a) Jacques, B.; Chavarot, M.; Rose-Munch, F.; Rose, E. Angew. Chem. 2006, 118, 3561. Angew. Chem., Int. Ed. 2006, 45, 3481. (b) Jacques, B.; Chanaewa, A.; Chavarot-Kerlidou, M.; Rose-Munch, F.; Rose, E.; Gerard, H. Organometallics 2008, 27, 626. (c) Jacques, B.; Eloi, A.; Chavarot-Kerlidou, M.; Rose-Munch, F.;

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Rose, E.; Gerard, H.; Herson, P. Organometallics 2008, 27, 2505. (d) Eloi, A.; Rose-Munch, F.; Rose, E.; Chavarot-Kerlidou, M.; Gerard, H. Organometallics 2009, 28, 925. (23) Cetiner, D.; Jacques, B.; Payet, E.; Chavarot-Kerlidou, M.; Rose-Munch, F.; Rose, E.; Tranchier, J.-P.; Herson, P. Dalton Trans. 2009, 27. (24) For the ortho-directing character of the Ph2P(O) group, see for instance: Ariffin, A.; Blake, A. J.; Ewin, R. A.; Li, W. S.; Simpkins, N. S. J. Chem. Soc., Perkin Trans. 1 1999, 3177. (25) For the ortho-directing character of the Me2NCH2 group, see for instance: Dickens, P. J.; Gilday, J. P.; Negri, J. T.; Widdowson, D. A. Pure Appl. Chem. 1990, 62, 575. (26) Details of the X-ray structure analyses of 15, 33, 34, and 38 are gathered in the Supporting Information. Deposition numbers: CCDC 813087 (15), 813088 (33), 813089 (34), 812997 (38). (27) Unpublished results. (28) (a) Di Renzo, G. M.; White, P. S.; Brookhart, M. J. Am. Chem. Soc. 1996, 118, 6225. (b) Hayashi, T. Acc. Chem. Res. 2000, 33, 354. (29) Viciu, M. S.; Germaneau, R. F.; Navarro-Fernandez, O.; Stevens, E. D.; Nolan, S. P. Organometallics 2002, 21, 5470. (30) Viciu, M. S.; Navarro, O.; Germaneau, R. F.; Kelly, R. A., III; Sommer, W.; Marion, N.; Stevens, E. D.; Cavallo, L.; Nolan, S. P. Organometallics 2004, 23, 1629. (31) Wencel, J.; Laurent, I.; Toupet, L.; Crevisy, C.; Mauduit, M. Organometallics 2010, 29, 1530. (32) (a) Braunstein, P.; Naud, F.; Dedieu, A.; Rohmer, M.-M.; De Cian, A.; Rettig, S. Organometallics 2001, 20, 2966. (b) Braunstein, P.; Zhang, J.; Welter, R. Dalton Trans. 2003, 507. (c) Zhang, J.; Braunstein, P.; Welter, R. Inorg. Chem. 2004, 43, 4172. (33) Barloy, L.; Ramdeehul, S.; Osborn, J. A.; Carlotti, C.; Taulelle, F.; De Cian, A.; Fischer, J. Eur. J. Inorg. Chem. 2000, 2523. (34) First example of a fully characterized crystalline (η1-allyl)Pd complex with an additional bidentate ligand: Kollmar, M.; Helmchen, G. Organometallics 2002, 21, 4771. (35) Pregosin, P. S.; Salzmann, R. Coord. Chem. Rev. 1996, 155, 35. (36) Faller, J. W.; Wilt, J. C. Organometallics 2005, 21, 5076. (37) Kuhn, O.; Mayr, H. Angew. Chem., Int. Ed. 1999, 38, 343 and references therein. (38) Work is in progress to survey in detail the electronic influence of the η5 system on the phosphorus atom according to the position of the P atom on the π ring. (39) Allen, D. W.; Taylor, B. F. J. Chem. Soc., Dalton Trans. 1982, 51. (40) Allen, D. W.; March, L. A.; Nowell, I. W. J. Chem. Soc., Dalton Trans. 1984, 483. (41) Muller, A.; Otto, S.; Roodt, A. Dalton Trans. 2008, 650. (42) These results are part of the work from our former Ph.D. student, D. Cetiner, who defended her Thesis on September, 30, 2010 at Paris 6 University. (43) For nonmetallocene ligands with only planar chirality see for example: (a) Jang, H. Y.; Seo, H.; Wook Han, J.; Chung, Y. K. Tetrahedron Lett. 2000, 41, 5083 and references therein. (b) Nelson, S. G.; Hilfiker, M. A. Org. Lett. 1999, 1, 1379. (44) Chiral diamines having a C2 axis of symmetry are an efficient tool for the asymmetric formation and resolution of aminals of ortho-substituted (benzaldehyde)Cr(CO)3 complexes: Alexakis, A.; Mangeney, P.; Marek, I.; Rose-Munch, F.; Rose, E.; Semra, A.; Robert, F. J. Am. Chem. Soc. 1992, 114, 8288. (45) (a) Tani, K.; Brown, L. D.; Ahmed, J.; Ibers, J. A.; Yokota, M.; Nakamura, A.; Otsuka, S. J. Am. Chem. Soc. 1977, 99, 7876. (b) Roberts, S. K.; Wild, S. B. J. Am. Chem. Soc. 1979, 101, 6254. (c) Mino, T.; Tanaka, Y.; Hattori, Y.; Yabusaki, T.; Saotome, H.; Sakamoto, M.; Fujita, T. J. Org. Chem. 2006, 71, 7346. (46) For the stereochemical description of the (η5-cyclohexadienyl)Mn(CO)3 complexes, see ref 22c. In the present study, the chirality of the complexes has been described by the configuration at the 3542


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chiral plane together with the configuration of the chiral auxiliary when present on the molecule. (47) (a) Eloi, A.; Rose-Munch, F.; Rose, E. J. Am. Chem. Soc. 2009, 131, 14178. (b) Rose-Munch, F.; Rose, E. Org. Biomol. Chem. 2011, DOI: 10.1039/c1ob05137g. (48) Chung, Y. K.; Williard, P. G.; Sweigart, D. A. Organometallics 1982, 1, 1053.

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Synthesis and Application in Catalysis of Planar Chiral - American

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