Organometallics 1995, 14,2353-2360
2353
Alkoxycarbonylation Reaction Involving a Tandem 1,3=MetalShift across Conjugated Allyl and Alkyne Bonds Kwei-Wen Liang,? Gene-Hsiang Lee,$ Shie-Ming Peng,$ and Rai-Shung Liu*>+ Departments of Chemistry, National Tsing-Hua University, Hsinchu 30043, Taiwan, Republic of China, and National Taiwan University, Taipei 10764, Taiwan, Republic of China Received January 9, 1995@ The reaction between CpW(C0)3Na and l-chlorohex-2-en-4-ye (1;&/trans = 1/4) gave CpW(C0)3(q1-hex-2-en-4-yn-l-yl) (2)in good yield (cisltrans = 1/41. The cis/truns isomers of 2 were separated on a silica column at 0 "C. Treatment of the trans isomer 2a with TCNE gave the [3+ 21 cycloaddition product exclusively to retain the ql-allyl activity. Addition of CF3S03H (1.1equiv) to 2a in cold diethyl ether in the presence of CH30H gave CpW(CO)3(y1-trans-4-oxo-2-hexen-l-yl) (5) in 61% yield. Stirring of 2a with RXH (RXH = H20, MeOH, MezCHCH2NH2) in THF over Florisil at 30 "C led to a new carbonylation to give CPW(CO)~(y3-l-syn-COXR-l-anti-Me-3-syn-vinylallyl) compounds (RX = OH (6), M e 0 (7), Me2CHCH2NH ( 8 ) )in 52- 18% yields. The reaction of CpW(C0)3Na and l-chloro-8-hydroxy-2-octen4-yne gave the corresponding +allyl compound which on a silica column produced the intramolecular alkoxycarbonylation product 13 in moderate yield. In the presence of BFyEt20, compound 7 reacted with aldehydes and unsaturated enones to give y4-dienesalts, which after demetalation by Me3NO liberated organic products in 40-55% isolated yields.
Introduction
Scheme 1
Metal-+allyl,l - q l - p r ~ p a r g y l , ~and , ~ -+allenyl compounds2v3are important in both organic and organometallic reactions. The reactions of these unsaturated yl-hydrocarbyl ligands with e l e c t r o p h i l e ~are ~,~~~~~ recognized to be useful processes for forming carbonI ' -7 M M carbon bonds in organic synthesis. One important feature of these compound is the presence of a 1,3-metal Metal-mediated alkoxylcarbonylation is a useful reacshift (Scheme 1)that shows a significant influence on tion in organic s y n t h e s i ~ In . ~ ~the ~ presence of acid electrophilic regi~chemistry.l-~ Direct evidence of these catalysts, CpW(C0)3(y1-propargy1) reacted smoothly metal shifts is well documented for both main-groupwith alcohols to give allyl compounds in which alkoxymetal and transition-metal complexe~.l-~The shift carbonylation occurred at the cental propargyl c a r b ~ n . ~ ? ~ proceeds more rapidly for more electropositive metals according to experimental and theoretical e v i d e n ~ e . ~ , ~ In contrast, the reaction of CpW(C0)3(y1-allenyl)8with alcohols, under the same conditions, produced a 1-(alkoxNational TsingHua University. National Taiwan University. Abstract published in Advance ACS Abstracts, April 1, 1995. (1) For the chemistry and application of metal-allyl compounds, see the review paper by: Yamamoto, Y.; Asao, N. Chem. Rev. 1993, 93,2207. (2)For main-group-metal allenyl and propargyl compounds, see the representative examples: (a) Seyferth, D.; Son, D. Y.; Shah S. Organometallics 1994, 13, 2105. (b) Brown, H. C.; Khire, U. R.; Racherla, U. S. Tetrahedron Lett. 1993,34,15.(c) Danheiser, R. L.; Carini, D. J. J . Org. Chem. 1980,45,3925.(d) Boaretto, A.; Marton, D.: Taeliavini. G. J. Ormnomet. Chem. 1986.297.149.(e) Marshall. J. A.;%ang, X.-J. J . OFg. Chem. 1991,56, 3212.if7 Marshall, J. A.f Wang, X. J. J . Org. Chem. 1991,56,6264. (3)For transition-metal propargyl and allenyl compounds, see: (a) Bell, P. B.; Wojcicki, A. Inorg. Chem. 1981,20, 1585. (b) Raghu, S.; Rosenblum, M. J . Am. Chem. SOC.1973,95,3060.(c) Pu,J.; Peng, T. S.; Arif, A. M.; Gladysz, J. A. Organometallics 1992,11, 3232. (d) Blosser, P. W.; Shimpff, D. G.; Gallucci, J. C.; Wojcicki, A.Organometallics 1993,12,1393.(e) Keng, R.-S.; Lin, Y.-C. Organometallics 1990, 9,289.(g) Benaim, J.;Merour, J.-Y.; Roustan, J . L. C. R. Acad. Sci. Paris, Ser. C 1971,272,789. (4)(a)Clark, T.; Rohde, C.; Schleyer, P. v. R. Organometallics 1983, 2, 1344.(b) Buhl, M.; Schleyer, P. v. R.; Ibrahim, M. A.; Clark, T. J . Am. Chem. SOC.1991,113,2466. ( 5 ) Gridnev, I. D.; Gurskii, M. E.; Ignatenko, A. V.; Bubnov, Y. N. Organometallics 1993,12,2487. +
$
@
(6)(a) Heck, R. F.; Wu, G.; Tao, W.; Rheingold, A. L. In Catalysis of Organic Reactions; Blackburn, D. W., Ed.; Marcel Dekker: New York, 1990;p 169.(b) Heck, R. F. Org. React. 1982,27,345.(c) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Application o f Organotransition Metal Chemistry; University Science Books: Mill Valley, CA, 1987;Chapter 12,p 619.(d) Hegedus, L. S. Transition Metals in the Synthesis of Complex Organic Molecules; University Science Books: Mill Valley, CA, 1994;Chapter 4,p 103. (7)For representative examples of catalytic alkoxycarbonylation, see: (a) Murray, T. F.; Norton, J. R. J. Am. Chem. SOC.1979,101, 4107.(b) Semmelhack. M. F.: Brickner. S. J. J A m . Chem. SOC.1981. 103,3945.(c) Matsuda, I.; O&o, A.; Sato, S. J . Am. Chem. SOC.1990; 112,6120.(d) Negishi, E.I.; Sawada, H.; Tour, J. M.; Wei, Y. J . Org. Chem. 1988,53,913.(e) Zhang, Y.; Negishi, E. I. J . Am. Chem. SOC. 1989,11 I , 3454.(0Tsuji, Y.; Kondo, T.; Watanabe, Y. J . Mol. Catal. 1987,40,295. (g) Jager, V.; Hummer, W. Angew. Chem., Znt. Ed. Engl. 1990,29,1171. (8)Tseng, T.-W.; Wu, I.-Y.; Lin, Y.-C.; Chen, C.-T.; Chen, M.-C.; Tsai, Y.-J.; Chen, M.-C.; Wang, Y. Organometallics 1991,10,43. (9)(a) Collin, J.; Charrier, C.; Pouet, M. J.; Cadiot, P.; Roustan, J. L. J . Organomet. Chem. 1979,168.321. (b) Roustan, J. L.: Merour, J. Y.; C h a k e r , C.; Benaim, J.; Cadiot, P. J . Organomet. Chem. 1979, 169, 39.(c) Charrier, C.; Collin, J.; Merour, J. Y.; Roustan, J . L. J . Organomet. Chem. 1978,162,57. (d) Cheng, M.-H.; Ho, Y.-H.; Lee, G.-H.; Peng, S.-M.; Liu, R.-S. J. Chem. Soc., Chem. Commun. 1991, 697.
0276-7333/95/2314-2353$09.00/0 0 1995 American Chemical Society
Liang et al.
2354 Organometallics, Vol. 14, No. 5, 1995
Scheme 2"
CO-M
-
+ ROH
\=e=
COz R' a
M = CpW(CO)2.
Scheme 3
=\=-7 M
M\=
Scheme 4"
c'
p1-ML(Co)Na M
(
C 0 l a
M(cO)-
F Me+
Figure 1. ORTEP drawing of compound 3. Me
Table 1. Selected Bond Distances (A)and Angles (deg)for 3
2b CN C N
w-c1
CN
w-c2 w-c3 w-c4
c1-01 2a
3 (67%)
c2-02 C3-03 c4-c5 C4-C8 C5-C6 c5-c9 C6-C7
4 (5 Yo)
I
co a
M = CpW(CO)2.
c1-w-c2
c1-w-c3
ycarbony1)allyl compound as depicted in Scheme 2. In a continuing effort to explore the synthetic utility of tungsten-propargyl compounds,10 we reportll here a novel alkoxycarbonylation reaction, the mechanism of which is initiated by uncommon tandem l,3-shifts of the metal fragment across conjugated allyl and alkyne bonds, as shown in Scheme 3. Although this process might be involved in the reaction of BrCH&H=CHCCH with magnesium and zinc metals to give CHpCHCH= C-CHMBr (M = Mg, Zn),l2 no corresponding Vl-pent2-en-4-yn-1-yl compound was ever isolated.
Cl-W-C4 c2-w-c3 c2-w-c4 c3-w-c4
w-c1-01
w- c 2 - 0 2 W-C3-03 w-c4-c5 W-C4-C8 C5-C4-C8 C4-C5-C6 c4-c5-c9 C6-C5-C9 C5-C6-C7 C5-C6-C12
Results and Discussion Synthesis and Reaction Chemistry of 7'-Hex-2en-4-yn-1-ylSpecies 2. Similar to the case for common transition-metal allyl compounds, the reaction of CpW(C0)3Na and l-chlorohex-2-en-4-ye(1; translcis = 4/11 in cold THF (0 "C, 5 h) proceeded smoothly to give the corresponding +allyl compound 2 in reasonable yields (78%)with a trans (2a)lcis(2b)ratio of 44. Two isomers were separated by chromatographic elution on a silica gel (diethyl etherhexane, 1/1) column at 0 "C. Chromatographic elution of the mixtures on a silica column at 30 "C led to skeletal rearrangement of the yl-trans isomer 2a to a x-allyl compound (vide infra; Scheme 6). (10)Wang, S.-H.; Shu, L.-H.; Shu, H.-G.; Liao, Y.-L.; Wang, S.-L.; Lee, G.-H.; Peng, S.-M.; Liu, R.-S. J . Am. Chem. SOC. 1994,116,5967. (11)Preliminary communication of this paper: Liang, K. W.; Lee, G. H.; Peng, S. H.; Liu, R. S. J. Chem. SOC.,Chem. Commun. 1994, 2705. (12) (a) Gerard, F.; Miginiac, P. J . Organomet. Chem. 1978, 155, 271. (b) Dulcere, J. P.; Gore, J.; Roumestant, M. L. Bull. SOC. Chim. Fr. 1974, 1119.
1.919(13) 1.971(10) 1.987(11) 2.318(9) 1.192(15) 1.135(13) 1.143(13) 1.570(12) 1.514(13) 1.564(12) 1.489(14) 1.583(12) 75.6(5) 76.9(5) 134.6(4) 107.8(5) 78.2(3) 76.8(4) 177.5(10) 173.4(10) 177.8(9) 119.4(6) 117.7(6) 99.3(7) 102.3(6) 117.7(7) 110" 101.8(7) 111.0(8)
1.491(15) 1.480(13) 1.567(13) 1.500(14) 1.455(15) 1.153(14) 1.454(15) 1.118(14) 1.142(13) 1.120(14) 1.128(15)
C6-Cl2 C6-Cl3 C7-C8 C7-Cl4 C7-Cl5 c9-c10 c10-c11 C12-N1 C13-N2 C14-N3 C15-N4 C5-C6-C13 C7-C6-C12 C7-C6-C13 C12-C6-C13 C6-C7-C8 C6-C7-C14 C6-C7-C15 C8-C7-C14 C8-C7-C15 c14-c7-c15 C4-C8-C7 C5-C9-C10 C9-ClO-C11 C6-Cl2-Nl C6-C13-N2 C7-C14-N3 C7-C15-N4
109.2(7) 111.4(7) 113.2(8) 110.0(8) 104.5(7) 112.4(8) 110.9(7) 110.1(7) 111.4(8) 107.6(8) 107.5(7) 178.6(10) 178.8(11) 178.9(10) 176.9(10) 176.6(10) 174.5(12)
The trans isomer 2a retains the chemical reactivity of +allyl compounds13 and undergoes [3 21 cycloaddition with TCNE to give 3 as the major product (67%) with a small amount of 4 (5%) affer separation by column chromatography. For 3,only one stereoisomer was detected in the lH NMR spectra (CDCld, which was assumed to be the trans isomer according to the related chemistry of metal $-allyl compounds.12J3 It is difficult to elucidate the stereochemistry from lH NOE difference spectra because the 'H NMR chemical shifts of the four ring protons are close to each other. We determined the structure of 3 by means of X-ray diffraction measurements. Figure 1shows the ORTEP drawing of 3,with selected bond distances and angles being provided in Table 1. The ORTEP drawing con-
+
~
~
(13)(a) Watkins, J. C.; Rosenblum, M. Tetrahedron Lett. 1994,25, 2097. (b) Buchester, A.; Klemarczyk, P.; Rosenblum, M. Organometallics 1982,1 , 1697. ( c ) Baker, R.; Moms,M. D.; Tunner, R. W. J. Chem. SOC.Chem. Commun. 1994,987.
A 1,3-Metal Shiftacross Allyl and Alkyne Bonds
Organometallics, Vol. 14, No. 5, 1995 2355
Scheme Sa
.
c10
I
0
A
w = CpW(C0)z.
w
Scheme 6"
4
2a+2b
2a
a
+
RXH
3 '
c q ~+ 2 b
silica
5
Florisil 30' C
'
R X= OH 6(52%); M e 0 7(36%) Me2CHCH2NH 8(18%)
w = CpW(C0)2.
firms the formation of a five-membered ring with the CpW(CO)3 and alkyne groups trans to each other. The five carbon-carbon bond distances of the five-membered ring lie within the range 1.489(14)-1.583(12) A, consistent with single carbon-carbon bonds. Compound 2a is prone to hydrolysis to convert its alkyne group to methylene ketone. Treatment of 2a with CF3S03H (1.1equiv) in cold diethyl ether (-40 "C) in the presence of excess MeOH delivered the $-trans4-oxo-2-hexen-1-yl compound 5 in 65% yield; the reaction was complete within 1h. During the workup, we did not find any cationic tungsten species as byproducts. In organic chemistry, acid-catalyzed hydration of an organic alkyne to a ketone is practical but requires severe conditions (concentrated HzS04,23 "C)14because the resulting vinyl cation intermediate is not energetically fa~orab1e.l~ The rapid hydration a t low temperature in the present work is attributed to formation of the y2-vinylallene cation A to further stabilize the resulting vinyl cation. Further attack of MeOH at A generates the y1-4-methoxypenta-2,3-dien-l-yl species B, which is expected to give 5 after subsequent acidcatalyzed hydrolysis. Although the allyl group of 2a reacted well with TCNE, the alkyne group is more reactive toward the proton than the allyl group. Carbonylation Reaction through a Tandem 1,3Metal Shift. We attempted first to separate the cis and trans isomers of 2 on a silica column at 30 "C but obtained the new organometallic compound 6 at the expense of the trans isomer; in this case compound 6 and the cis isomer 2b were obtained in 38% and 11% yields, respectively. The fact that 2b was inactive toward a silica column at 30 "C was confirmed in a separate test. lH NMR and IR spectra of 6 indicate that the compound has a CpW(CO)z(n-allyl)structure with the presence of vinyl, methyl, and carboxylic acid groups. This information revealed a considerable structural rearrangement in the conversion of 2a to 6. The molecular structure of 6 was determined by X-ray diffraction measurements, and its ORTEP drawing is (14)(a) Crammer, P.; Tidwell, T. T. J. Org. Chem. 1981,46,2683. (b)Allen, A. D.; Chiang, Y.; Kresge, A. J.; Tidwell, T. T. J. Org. Chen. 1982,47, 775. (15)Kohler, H. J.; Lischka, H. J . Am. Chem. SOC.1979,101,3479.
c9
Figure 2. ORTEP drawing of compound 6. Table 2. Selected Bond Distances (A) and Angles (deg)for 6
w-c1
w-c2 w-c5 W-C6 w-c7 c1-01 c2-02 c3-c4 c1-w-c2 Cl-W-C5 C1- W-C6 c1-w-c7 c2-w-c5 C2-W-C6 c2-w-c7 C5-W-C6 c5-w-c7 C6-W-C7
w-c1-01
w-c2-02 c3-c4-c5 w-c5-c4
1.959(8) 1.942(8) 2.391(8) 2.206(7) 2.354(7) 1.140(9) 1.155(10) 1.301(11) 80.0(3) 72.4(3) 105.5(3) 108.6(3) 114.7(3) 108.3(3) 74.1(3) 35.65(23) 61.59(24) 35.5(3) 178.4(8) 179.8(7) 124.5(8) 118.8(6)
c4-c5 C5-C6 C6-C7 C7-C8 c7-c9 (28-03 C8-04 W-C5-C6 C4-C5-C6 W-C6-C5 W-C6-C7 C5-C6-C7 W-C7-C6 W-C7-C8 w-c7-c9 C6-C7-C8 C6-C7-C9 C8-C7-C9 C7-C8-03 C7-C8-04 03-C8-04
1.453(11) 1.418(9) 1.399(10) 1.482(9) 1.528(11) 1.231(9) 1.307(9) 65.0(4) 123.5(7) 79.3(4) 78.0(4) 119.2(6) 66.4(4) 113.5(5) 117.4(4) 119.3(6) 121.0(6) 111.7(6) 121.6(6) 116.0(6) 122.5(6)
provided in Figure 2, with selected bond distances and angles being given in Table 2. The ORTEP drawing confirms the formation of a tungsten-n-allyl group with the vinyl and COOH groups in syn positions and the methyl group in an anti position. This structure may be envisaged by considering that one of the three carbonyls of 2a has been attacked by HzO to give W-ylCOzH, which subsequently adds to the CMe carbon of the ligand; the remaining CpW(CO)2fragment migrates to the original alkyne fragment to form a n-allyl complex. Compound 6 has an e m conformation; i.e. the allyl mouth faces awa from the cyclopentadienyl group. The W-C5 (2.391(8) ), W-C6 (2.206(7)A), and W-C7 (2.354(7) A) bond lengths represent normal tungstenx-allyl distances. The eight atoms including C3-C8, 0 3 , and 0 4 were uite planar within a maximum deviation of 0.17(1) ; this orientation is favorable for electron delocalization over the vinyl, carboxylate carbonyl, and allyl fragments. We examined the carbonylation reaction of 2a with alcohol and amine. Chromatographic elution of 2a through a silica column (30 "C) with methanol and isobutylamine is ineffective at inducing carbonylation, and in each case 2a was recovered exclusively. We found a n effective method involving stirring of a THF
1
x
Liang et al.
2356 Organometallics, Vol. 14,No. 5, 1995
Scheme 7" 2a
a
w = CpW(C0)2. Scheme 8"
-
OSiMez (t-Bu) BuLi (-78OC) acrolein
1
T ) - A OSiMez (t-Bu) nu 9 1 ( 1 ) MsCI, 2,6-lutidine V..
W(C0)Na
12
'
U
13 = w = CpW(C0)2.
solution of 2a with H20, MeOH, or isobutylamine over predried Florisil (250 " C , 12 h, Torr) a t 30 "C, to give 6, 7, and 8 in 52%, 36%, and 18%yields, respectively. The cis isomer 2b was inactive under the same conditions. Spectral data for 7 and 8 are fully consistent with the attributed structure given in Scheme 6. To account for the formation of 6, we propose that, with Florisil as catalyst, the CpW(COh fragment of 2a first undergoes 1,3-allyl migration to give gl-l-hexen4-yn-3-yl intermediate C,but this intermediate gives a 2-carboxylated allyl compound rather than 6 (vide supra; Scheme 2). Further 1,3-CpW(CO)3migration to the gl-2,3,5-hexatrien-2-y1 species D is necessary t o achieve alkoxycarbonylation at the CMe carbon. Although alkoxycarbonylation of the gl-allenyl compound has been previously reported, the mechanism was neglected. In our proposal, formation of 6 is envisaged by considering that one of the three CO groups of D is attacked by H2O to form E, which after reductive elimination produces the anion F. Further protonation of F will give the observed product. To achieve the most stable configuration, the structure is expected to have the COOH and vinyl groups in syn positions to minimize interligand steric hindrance. An alternative possibility for the formation of F involves insertion of CO into the W-a-allenyl bond of D, followed by H20 attack as depicted in Scheme 7. This mechanism (Scheme 7) is operable only in the presence of Florisil and silica gel rather than basic alumina. Silica gel is commonly employed in organic reactions16 as an acidic catalyst; its function is very specific such that it cannot be replaced by another (16)(a)Hojo, M.; Masuda, R. Synth. Commun. 1975,5,169. (b) Hojo, M.; Masuda, R. Tetrahedron Lett. 1976, 613. (17)(a) Regen, S. L.; Koteel, C. J.Am. Chem. SOC.1977, 99,3837. (b) Mckillop, A.; Young, D. W. Synthesis 1979, 401.
catalyst.l' We tested the above carbonylation with some acidic catalysts, including BF3eEt20, TiC14, and ZnCl2, but 2a was recovered exclusively in every case. Although the roles of Florisil and silica gel remain unclear, we believe that the carbonylation is a surface reaction which requires a widely acidic surface area to initiate the reaction. The cis isomer 2b was inactive toward H20, MeOH, and isobutylamine even when Florisil was employed. According to theoretical calculations, the first 1,3-metal shift across the allyl group involves a n-allyl-like intermediate (Scheme 1). Therefore, the inactivity of the cis isomer 2b is attributed to increasing steric hindrance between CpW(CO)3 and the methyl groups of this n-allyl transition structure. Intramolecular Alkoxycarbonylation though a Tandem 1,3-MetalShift. To achieve intramolecular carbonylation, we prepared l-chloro-8-((tert-butyldimethylsilyl)oxy)-2-octen-4-yne(10;trans /cis = 5/1) according to Scheme 8. The trans isomer of 10 was isolated in pure form (62%) after chromatographic purification. Similar to 2, the cis isomer of 10 is not a useful material for carbonylation. Treatment of 10 with B a F (2.0 equimolar) in THF at 23 "C for 1h afforded the alcohol 11 in 57% yield. The reaction of CpW(C013Na and 11 proceeded smoothly under ambient conditions (23 "C,4 h) to give the gl-allyl compound 12 as monitored by lH NMR spectra. Attempts to purify 12 by chromatographic elution were unsuccessful even at 0 "C, due to its intrinstic tendency to undergo intramolecular cyclization. Therefore, the gl-allyl intermediate was converted directly to 13 on elution through a silica column at 23 "C; the yield of 13 was 51%. Compound 13 could also be prepared directly from CpW(CO)3 and 10 in THF (23 "C, 3 h), followed by treatment with B u N F (1.8 equiv, 23 "C, 3 h) and column elution (23 "C);the yield was 35%. In the two
Organometallics, Vol. 14, No. 5, 1995 2357
A 1,3-Metal Shift across Allyl and Alkyne Bonds
W
Figure 3. ORTEP drawing of compound 13. Table 3. Selected Bond Distances (A) and Angles (deal for 13
w-c1
w-c2 w-c5 W-C6 w-c7 c1-01 c2-02 c3-c4 c4-c5
1.934(14) 1.927(12) 2.409(15) 2.224(12) 2.422(13) 1.166(17) 1.161(15) 1.303(23) 1.392(23)
c1-w-c2 c1-w-c5 C1-W-C6 c1-w-c7 c2-w-c5 C2-w-C6 c2-w-c7 C5-W-C6 c5-w-c7 C6-W-C7 w-(21-01 w-c2-02 c3-c4-c5 w-c5-c4 W-C5-C6 C4-C5-C6
80.6(5) 69.9(5) 104.3(5) 114.5(5) 109.8(5) 110.3(5) 76.6(5) 35.1(5) 62.3(5) 37.3(5) 177.7(12) 178.2(10) 122.9(17) 122.9(12) 65.3(8) 123.1(15)
C5-C6 C6-C7 C7-C8 C7-Cll C8-C9 C9-ClO (210-03 (211-03 Cll-04 W-C6-C5 W-C6-C7 C5-C6-C7 W-C7-C6 W-C7-C8 w-c7-c11 C6-C7-C8 C6-C7-Cll C8-C7-Cll C7-C8-C9 C8-C9-C10 C9-C10-03 C7-Cll-03 C7-Cll-04 03-Cll-04 C10-034211
1.407(21) 1.498(19) 1.514(17) 1.431(17) 1.438(23) 1.44(3) 1.375(19) 1.364(15) 1.215(16) 79.7(8) 78.6(7) 118.8(12) 64.1(6) 118.4(9) 107.6(8) 119.3(11) 113.1(11) 120.9(12) 109.2(12) 115") 113.0(14) 117.9(11) 127.8(12) 114.3(11) 120.1(11)
reactions above, we obtained no v3-allyl acid compound from the intermolecular carboxylation of 12 with water from silica. The latter is slower than intramolecular alkoxycarbonylation reactions. The molecular structure of 13 is presented in Figure 3, with selected bond distances and angles being provided in Table 3. Similar to 6,compound 13 has an ex0 conformation with the allyl mouth opposite the cyclopentadienyl group; the vinyl and lactonyl carbonyl groups are in syn positions with respect to the allyl group. The six-membered lactone ring approaches a distorted-boat conformation with the C l l - 0 4 (1.215(16) and C l l - 0 3 (1.364(15)A)lengths representing carbon-oxygen double and single bonds, respectively. The allyl C5-C6 (1.407(21) A) and C6-C7 (1.498(19) 8)bond lengths are asymmetric, whereas the C4-C5 length (1.392(23) A) is significantly shorter than that of a normal carbon-carbon length (1.54 8). This information demonstrates electron delocalization between the vinyl and allyl groups. The dihedral angles defined by the C7-Cll-O4/allyl planes and C3-C4CUallyl planes are 13.7(15) and 19.5(19)",respectively,
A)
indicative of electron delocalization through the C8C11 and 0 4 unsaturated fragment. BFs-Promoted Addition of Aldehydes and Enones to 7. These alkoxycarbonylation products belong to the class of y3-pentadienyl compounds; they are expected to be reactive toward electrophiles in the presence of a Lewis acid.laJg To demonstrate its synthetic utility, as shown in Scheme 9, we treated compound 7 with aldehydes RCHO (R = Ph, MezCH; 1.5 equiv) in the presence of BFyEtzO (1.0 equiv) in cold diethyl ether, yielding an orange insoluble precipitate, presumably the v4-dienesalts G.19,20 The salts were unstable above -40 "C, and organic compounds 14 and 15 were gradually liberated. Spectral characterization of the salts was unsuccessful due to their thermal instability. Complete demetalation of the salts was achieved with MesNO to liberate organic compounds 14 and 15 in 56% and 50% yields, respectively. The reactions between 7 and enones RCOCH=CHz (R = Me, Et) under the same conditions proceeded smoothly to give analogous diene salts H,which after demetalation gave ketone compounds 16 and 17 in 42% and 40% yields, respectively.
Experimental Section All operations were carried out under argon in a Schlenk apparatus or in a glovebox. The solvents benzene, diethyl ether, tetrahydrofuran, and hexane were dried with sodium benzophenone and distilled before use. Dichloromethane was dried over calcium hydride and distilled. Organic ligands 1 and 5-((tert-butyldimethylsilyl)oxy)-l-pentynewere prepared according t o the procedures in the literature.21 All 'H NMR (400 and 300 Hz) and 13C NMR (100 and 75 MHz) spectra were obtained on either a Bruker AM-400 or a Varian Gemini-300spectrometer; the chemical shifts of 'H and 13CNMR are reported relative to tetramethylsilane(6 0 ppm). Elemental analyses were performed at National Cheng Kung University, Tainan, Taiwan, Republic of China. Infrared spectra were recorded on a Perkin-Elmer 781 spectrometer. High-resolution mass spectra were recorded on a JEOL HX 110 spectrometer. (a)Synthesis of CpW(CO)s(~l-hex-2-en-4-yn-l-y1) (2a (transIsomer) and 2b (cis Isomer). To a THF solution (100 mL) of W(CO)6 (5.0 g, 14.4 mmol) was added NaCsH5 (C5H6 (0.94 g, 14.2 mmol), Na (0.34 g, 14.4 mmol), THF (20 mL)), and the mixtures were heated under reflux for 3 days. To the yellow CpW(C0)3Nasolution was added l-chlorohex-2-en-4yne (1.65 g, 14.5 mmol) at 0 "C, and the solution was stirred for 4 h before being warmed t o 23 "C. After it was stirred for an additional 3 h at 23 "C, the solution was evaporated to dryness; the residues were eluted through a silica column at 0 "C with diethyl etherhexane (1/2) as the eluting solvent. Two yellow bands were developed and collected to give 2a (trans isomer; Rf= 0.65, yellow solid, 3.68 g, 8.90 mmol) and 2b (cis isomer; Rf = 0.57, yellow oil, 0.95 g, 2.30 mmol, 16%), respectively. Data for 2a: IR (neat, cm-l) v ( C W ) 2189 (w),v(C0) 2009 (s), 1914 (s), v(C=C) 1635 (w);'H NMR (400 MHz, CDCls) 6 1.86 (d, J = 2.1 Hz, 3H, Me), 2.35 (d, 2H, J = 8.8 Hz, W-CHZ), 5.13 (dq, lH, J = 15.2,2.1 Hz, =CHC=), 5.33 (s,5H, Cp), 6.28 (dt, J = 15.2, 8.8 Hz, lH, W-CH&H=); 13CNMR (100 MHz, CDC13) 6 -7.6 (W-CHz), 4.4 (Me), 79.1 and 88.4 ( C W ) , 92.4 (18)Lin, S. H.; Yang, Y. J.; Liu, R. S. J. Chem. SOC.,Chem. Commun.
1991, 1004. (19) Cheng, M.-H.; Yang, G. M.; Chow, J. F.; Lee, G. H.; Peng, S. M.; Liu, R. S. J. Chem. SOC.,Chem. Commun. 1992, 934.
(20) Cheng, M. H.; Ho, Y. H.; Wang,S. L.; Peng. S. M.: Liu. R. S. J. Chem. SOC.Chem. Commun. 1992,45. (21)Corey, E. J.; Venkateswarlu, A. J.Am. Chem. SOC.1972, 94, 6190.
Liang et al.
2358 Organometallics, Vol. 14,No. 5, 1995
Scheme 9" W+ W
0
OH R=Ph 14, 5 6 % Me2CH 15, 5 0 %
BF3 E t 2 0
H = w = CpW(C0)z.
13C NMR (100 MHz, CDCl3) 6 -8.9 (W-CHz), 8.6 (CH3), 33.6 (Cp), 114.6 (=CHCHz), 151.3 (=CHC=), 216.7 and 228.1 (3 (COCHZ), 92.1 (Cp), 121.7 (=CHCO), 156.6 (CHzCH=), 200.9 W-CO); mass (75 eV, mle) 384 (M+ - CO), 356 (M+ - 2CO). (CO), 216.7 and 228.1 (3 W-CO); mass (75 eV, d e ) 402 (M+ Anal. Calcd for C14H12WO3: C, 40.80; H, 2.94. Found: C, - CO). Anal. Calcd for C14H14W04: C, 39.07; H, 3.28. 40.48; H, 2.95. Found: C, 39.15; H, 3.35. Data for 2b: IR (Nujol, cm-l) v(CEC) 2179 (w), v(C0) 2004 (d) Synthesis of CpW(CO)z(qs1-syn-carboxy-l-anti(s),1920 (s), v(C=C) 1631 (w); IR (neat, cm-') v(C0) 2008 (s), methyl-3-syn-vinylallyl)(6). Method A. A crude mixture 1918 (8); 'H NMR (300 MHz, CDC13) 6 2.04 (d, J = 2.1 Hz, of 2a and 2b (2.00 g, 4.80 mmol, 2d2b = 4/1) was chromato3H, Me), 2.60 (d, J = 9.1 Hz, 2H, W-CHZ), 5.00 (dq, J = 10.4, graphed through a silica column at 30 "C with diethyl ether/ 2.1 Hz, l H , =CHC=), 5.48 ( s , 5H, Cp), 6.33 (dt, l H , J = 10.4, hexane (1/2) as eluent. A yellow band was collected to produce 9.1 Hz, =CHCHz); 13CN M R (75 MHz, CDCl3) 6 -9.8 (W-CHz), 2b (Rf0.57)as a yellow oil (0.23 g, 0.53 mmol, 11%).After 2b 4.7 (Me), 90.6 and 91.2 (CEC), 92.4 (Cp), 100.6 (=CHCHz), was eluted, the top immobile band was eluted with diethyl 151.6 (d, =CHC=), 217.1 and 228.3 (3 W-CO); mass (75 eV, etherhexane (2L) to give a dark yellow band (Rf 0.31) that mle)384 (M+- CO), 356 (M+ - 2CO). Anal. Calcd for C14H12afforded 6 as a yellow solid (0.78 g, 1.82 mmol, 38%). W03: C, 40.80; H, 2.94. Found: C, 40.51; H, 3.02. Method B. Florisil (8.5 g) was heated in vacuo (250 "C, (b) Cycloaddition of 2a with TCNE. To 2a (0.18 g, 0.45 1.0 x 10-4 Torr) for 12 h, and this solid was treated with THF mmol) in THF (5 mL) was slowly added a THF solution (3 mL) (20 mL) and HzO (0.50 mL) after it was cooled to 23 "C. To of TCNE (58 mg, 0.45 mmol) at 0 "C. After the mixture was this THF-Florisil mixture was added a THF solution (15 mL) stirred for 30 min, the resulting green solution was brought of 2a (0.25 g, 0.60 mmol); the resulting solution was stirred to dryness and chromatographed through a silica column with at 30 "C for 1h. After removal of the solvent, the wet Florisil diethyl etherhexane (1l1)as the eluting solvent. Two bands solid was placed on top of a silica column immersed with were developed and collected to give 3 (Rf= 0.42, yellow solid, hexane. The column was fist eluted with diethyl etherhexane 0.16 g, 0.30 mmol, 67%) and 4 (Rf = 0.21, red solid, 12 mg, (ID) to remove impurities and subsequently eluted with 0.023 mmol, 5%),respectively. diethyl etherhexane (2/1)to produce a dark yellow band of 6 Data for 3: IR (Nujol, cm-') v(C=C) 2179 (w), v(CN) 2250 (0.78 g, 1.82 mmol, 38%). IR (Nujol, cm-l) v(OH) 3300-2700 (s), v(C0) 2022 (s), 1919 (s); 'H NMR (400 MHz, CDCl3) 6 1.95 (br, s), v(C0) 1932 ( s ) ,1876 ( s ) ,1652 ( s ) ,v(C=C) 1625 (w); 'H (d, J = 2.2 Hz, 3H, Me), 2.65 (dd, J = 14.1,12.3 Hz, lH, CHH'), NMR (400 MHz, CDC13) 6 1.30 ( s , 3H, Me), 3.10 (t, J = 10.0 2.86 (ddd, J = 12.3, 12.0, 8.2 Hz, l H , W-CH), 3.11 (dd, J = Hz, l H , HZ), 4.83 (d, J = 10.0 Hz, l H , H1), 4.89 (d, J = 10.0 14.1, 8.2 Hz, 1H, CHH'), 3.45 (dq, J = 12.0, 2.2 Hz, l H , Hz, l H , H4), 5.38 (d, J = 16.8 Hz, l H , H5), 5.41 ( s , 5H, Cp), CHWC), 5.66 (s, 5H, Cp); 13CNMR (100 MHz, CDC13) 6 1.4 5.83 (dt, J = 16.8, 10.0 Hz, l H , H3); 13C NMR (100 MHz, (W-CH),3.8(Me),45.0 and 52.6 (2 C-CN),53.4(CHH),55.9 CDC13) 6 16.7 (Me), 45.5 (CMe), 56.7 (CH2),67.2 (CHI), 93.7 (CHCe), 73.5 and 87.3 (CEC), 91.6 (Cp), 110.2 (CN), 110.5 (Cp), 138.5 (=CH3), 143.4 (=CH4), 181.3 (C=O), 227.1 and (CN), 111.3 (CN), 111.5 (CN), 216.4 (W-CO), 216.6 (W-CO), 226.5 (2 W-CO); mass (75 eV, mle) 430 (M+),402 (M+ - CO), C, 46.81; H, 223.9 (W-CO). Anal. Calcd for CZZHIZN~WO~: 374 (M+ - 2CO). Anal. Calcd for C14H14W04: C, 39.10; H, 2.14; N, 9.93. Found: C, 46.95; H, 2.08; N, 9.65. 3.28. Found: C, 39.11; H, 3.35. Data for 4: IR (neat, cm-l) v(CN) 2220 (m), v(C0) 2019 (s), (e) Synthesis of CpW(CO)~(q3-l-syn-(methoxycarbo1922 (9); lH NMR (300 MHz, CsDd 6 1.05 (s,3H, Me), 1.92 (d, nyl)-l-anti-methyl-3-syn-vinylallyl) (7). This compound J = 9.5 Hz, 2H, W-CHz), 4.33 (s, 5H, Cp), 6.14 (d, J = 15.0 was prepared from 2a and MeOH over Florisil according t o Hz, l H , =CHC=), 6.44 (dt, J = 15.0, 9.5 Hz, lH, CHzCH=). synthetic procedures described in method B for compound 6; Anal. Calcd for C ~ Z H ~ ~ N ~C, W46.81; O ~ : H, 2.14; N, 9.93. the yield of 7 was 36%: IR (neat, cm-') v(C0) 1942 (s), 1860 Found: C, 46.99; H, 2.23; N, 9.91. Attempts to record 13CNMR (s), 1685 (m), v(C=C) 1625 (w); 'H NMR (300 MHz, CDC13) 6 spectra in dg-toluene were unsuccessful due t o the poor 1.28 (s, 3H, Me), 3.03 (t, J = 10.0 Hz, l H , H2), 3.66 (8, 3H, solubility and solution instability of 4 at 25 "C. (c) Synthesisof CpW(CO)~(q1-trans-4-oxo-2-hexen-l-yl)OMe), 4.82 (d, J = 10.0 Hz, l H , H4),4.86 (d, J = 10.0 Hz, l H , Hl), 5.37 (s, 5H, Cp), 5.36 (d, J = 16.2 Hz, lH, H5), 5.84 (dt, (5). To a solution of 2a (0.18 g, 0.45 mmol) in diethyl ether/ l H , J = 16.2, 10.0 Hz, H3); 13CNMR (75 MHz, CDC13) 6 16.7 CH30H (6 m u 3 mL) was added CF3S03H (0.40 mL, 0.45 (Me), 46.6 (CCHs), 51.8 (OMe), 56.2 (CH'), 66.6 (CHI), 93.4 mmol) at -40 "C, and the solution was stirred for 1h at the (Cp), 112.9 (=CH4H5),138.7 (=CH3), 176.0 (C=O), 227.2 and same temperature before addition of a saturated NaHC03 226.6 (2 W-CO); mass (75 eV) 444 (M+),416 (M+ - CO), 388 solution. The solution was concentrated to half its volume, (M+ - 2CO). Anal. Calcd for C15H16W04: C, 40.57; H, 3.63. and the organic layer was extracted with diethyl ether (2 x Found: C, 40.67; H, 3.62. 10 mL). The residue was eluted through a silica column to (0Synthesis of CpW(C0)2(q3-1-syn-((isobutylamino)produce a yellow band that yielded 5 as a yellow oil (0.12 g, carbonyl)-l-anti-methyl-3-syn-vinylallyl~ (8). This com0.28 mmol, 61%). IR (neat, cm-') v(C0) 2004 ( s ) ,1924 (s), 1668 pound was prepared from 2a and isobutylamine over Florisil (s), v(C=C) 1625 (m); 'H NMR (400 MHz, CDC13) 6 1.05 (t,J according to synthetic procedures described in method B for = 7.2 Hz, 3H, Me), 2.36 (d, J = 8.1 Hz, 2H, W-CHz), 2.48 (9, compound 6;the yield of 8 was 18%: IR (Nujol, cm-l) v(NH) J = 7.2 Hz, 2H, COCHz), 5.33 (s, 5H, Cp), 5.80 (d, J = 15.0 3363 (m), v(C0) 1935 ( s ) ,1853 (SI, 1630 (s); lH NMR (300 MHz, Hz, l H , =CHCO), 7.13 (dt, J = 15.0, 8.1 Hz, l H , CHzCH=);
A 1,3-Metal Shift across Allyl and Alkyne Bonds CDC13) 6 0.91 (d, 6H, J = 6.6 Hz, 2 Me), 1.24 (s, 3H, Me), 1.77 (m, 1H, CHMez), 2.89 (t, l H , J = 9.8 Hz H2), 3.06 (m, 2H, NHCHH'), 4.82 (d, J = 9.8 Hz, l H , H1), 4.97 (d, J = 10.0 Hz, l H , H4), 5.37 (s, 5H, Cp), 5.35 (d, J = 16.8 Hz, l H , H5), 5.84 (ddd, J = 16.8, 10.0,9.8 Hz, lH, H3);13CNMR (75 MHz, CDCl3) 6 17.0 (Me), 19.9 (Me), 20.2 (Me), 28.5 (CHMez),47.2 (NH-CHZ), 50.3 (CC=O), 55.4 (CW), 65.1 (CHI),93.7 (Cp), 112.5 (%H4H5), 139.1 (=CH3), 173.8 (C=O), 226.7 and 230.3 (2 W-CO); mass (75 eV, mle) 485 (M+),457 (M+ - CO), 429 (M+ - 2CO). Anal. Calcd for C18H22W03N: C, 44.65; H, 4.58; N, 2.88. Found: C, 44.48; H, 4.86; N, 3.01. (g) Synthesis of 3-Hydroxy-8-((tert-butyldimethylsilyl)oxy)-l-octen-4-yne(9). To 5-((tert-butyldimethylsilyl)oxy)-1-pentyne(9.0 g, 48.0 mmol) in THF was added BuLi (2.50 M, 19.2 mL, 48.0 mmol) at -78 "C, and the mixture was stirred for 2 h before it was transferred t o a THF (10 mL) solution of acrolein (3.40 g, 60.0 mmol) a t -40 "C. After it was stirred for 2 h, the solution was quenched with a saturated NH4Cl solution, concentrated, and extracted with diethyl ether (2 x 30 mL). The extract was concentrated, and flash chromatography (silica column, 1/1 diethyl etherhexane) of the residues afforded 9 as a colorless oil (10.9 g, 45.1 mmol, 94.0%): IR (neat, cm-l) v(C=C) 2128 (w), v(C=C) 1645 (w); 'H NMR (300 MHz, CDCl3) 6 0.05 (s, 6H, SiMez), 0.86 (s, 9H, SiMea), 1.69 (m, 2H, CHz CHZOSi), 1.93 (s, l H , OH), 2.30 (t, J = 6.7 Hz, 2H, =CCHz), 3.65 (t,J = 6.0 Hz, 2H, CHzOSi), 4.82 (dd, J = 5.4, 1.9 Hz, l H , CHOH), 5.16 (d, J = 10.1 Hz, l H , =CHH'), 5.40 (d, J = 17.0 Hz, l H , =CHH'), 5.95 (ddd, J = 17.0, 10.1, 5.4 Hz, l H , =CW; 13CNMR (75 MHz, CDC13) 6 -5.4 (SiMe), 15.2 (CHz), 18.3 (SiCMes), 25.9 (SiCMes), 31.7 (CHZCHzOSi), 61.6 (CHZOSi), 63.4 (CHOH), 86.8 and 79.1 (CrC), 115.9 (=CHz), 137.4 (=CHI. Anal. Calcd for C14H26SiOz: C, 66.10; H, 10.31. Found: C, 66.08; H, 10.40.
(h) Synthesis of 1-ChloroS-((tert-butyldimethylsily1)oxy)-2-octen-4-yne(10). To a mixture of 9 (2.24 g, 8.80 "01) and 2,6-lutidine (2.10 mL, 13.2 mmol) was added a DMF solution (50 mL) containing LiCl(0.38 g, 8.80 mmol), and the mixture was stirred at 0 "C for 0.5 h before methanesulfonyl chloride (1.48 mL, 13.2 mmol) was added. After it was stirred for 20 min a t 0 "C, the solution was heated at 80 "C for 10 min, cooled to 23 "C and then added to diethyl ether (150 mL) and water (50 mL). The organic layer was separated, washed with water (3 x 30 mL), and dried over MgS04 Removal of the solvent in vacuo afforded 10 as an oil (2.30 g, 8.40 mmol, translcis = 5/1). Chromatographic elution of the crude product through a silica column (diethyl etherhexane, 1/5)yielded the desired trans isomer as a colorless oil (1.5 g, 5.50 mmol, 62%). Data for the trans isomer: IR (neat, cm-l) v(C=C) 2158 (w), v(C=C) 1639 (w); 'H NMR (300 MHz, CDC13) 6 0.05 (s, 6H, SiMez), 0.89 (s, 9H, SiCMes), 1.72 (m, 2H, CHZCHzOSi), 2.30 (t, J = 6.5 Hz, 2H, ECCHZ),3.65 (t,J = 6.0 Hz, 2H, CHZOSi), 4.07 (d, J = 6.6 Hz, 2H, ClCHz), 5.75 (d, J = 17.0 Hz, l H , =CHC=), 6.14 (dt, J = 17.0,6.6 Hz, lH, =CHCHzCl); 13CN M R (75 MHz, CDCl3) 6 -5.4 (SiMe),15.8 (ECCHZ),18.3(SiC(CH&), 25.9 (SiCMeS),31.5 (CHZCHzOSi),44.2 (CHZCl),61.6 (CHOSi), 92.6 and 90.6 (C=C), 114.7 (=CHCHzCl), 137.4 (=CHCE). Anal. Calcd for C14H25SiC10: C, 61.73; H, 9.26. Found: C, 61.80; H, 9.30. (i) Synthesisof l-Cbloro-8-hydroxy-2-octen-4-yne (11). To a THF (10 mL) solution of 10 (1.50g, 5.50 mmol) was added B d F (2.87 g, 11.0 mmol), and the mixture was stirred at 1 h at 23 "C before addition of a saturated NaCl solution (10 mL). The organic layer was extracted with diethyl ether (3 x 20 mL), dried over MgS04, and concentrated in vacuo. Flash chromatography of the residues afforded 11 as a colorless oil (0.50 g, 3.14 mmol, 57%): IR (neat, cm-') v(C=C) 2158 (w), v(C=C) 1639 (w); lH NMR (300 MHz, CDC13) 6 1.72 (m, 2H, CHzCHzOH), 1.84 (br s, l H , OH), 2.30 (t, J = 6.5 Hz, 2H, CICCHZ), 3.65 (t, J 6.0 Hz, 2H, CHzOH), 4.07 (d, J = 6.6 Hz, 2H, CHZCl), 5.75 (d, J = 17.0 Hz, l H , =CHC=), 6.14 (dt, l H , J = 17.0, 6.6 Hz, =CHCHzCl); I3C NMR (75 MHz, CDC13) 6 15.8 (=CCHz), 31.5 (CHzCHzO), 44.0 (CHzCl), 61.2 (CHOH),
Organometallics, Vol. 14, NO.5, 1995 2359 92.1 and 90.6 (CEC), 114.5 (=CHCCl), 136.0 (=CHCE); HRMS calcd for C8HllClO 158.0498, found 158.0503. (i) Synthesis of 13. Method k To a THF (30 mL) solution of CpW(C0)3Na (ca. 2.80 mmol) was added 11 (0.40 g, 2.84 mmol) at 23 "C; the mixture was stirred for 4 h. Sampling of the solution (ca. 5 mL) for NMR measurement (300 MHz, CDC13) showed the presence of the ql-allyl compound 12 (6 2.14, J = 7.0 Hz, W-CHz). The solution was evaporated to dryness and chromatographed through a silica column (diethyl etherhexane, 1/11 a t 23 "C to produce an orange band (Rf0.48)of 13 (0.65 g, 1.43 mmol, 51%): IR (neat, cm-l) v(C0) 1947 (s), 1866 (s), 1695 (s), v(C=C) 1625 (m); lH NMR (400 MHz, CDCl3) 6 1.94-1.49 (m, 4H, CHZCHZCHZO),
3.19(t,1H,J=1O.1Hz,H2),4.41-4.18(m,2H,CHH'O),4.82 (d, J = 10.1 Hz, l H , H1), 5.03 (d, J = 10.1 Hz, l H , H4), 5.28 (d, J = 16.6 Hz, l H , H5), 5.36 (s, 5H, Cp), 5.84 (dt, l H , J = 16.6, 10.1 Hz, H3); 13C NMR (100 MHz, CDC13) 6 23.5 (CH2), 27.9 (CHz), 44.6 (CCO), 57.7 (CH'), 66.8 (CHI), 71.8 (CHHO), 94.2 (Cp), 113.9 (=CH4H5),138.2 (=CH3), 175.6 (COz), 231.8 and 227.1 (2 W-CO); mass (75 eV, mle): 456 (M+),418 (M+ CO), 390 (M+ - 2CO). Anal. Calcd for C16H16W04: C, 42.13; H, 3.54. Found: C, 42.17; H, 3.55. Method B. To a THF (40 mL) solution of CpW(C0)3Na(ca. 10 mmol) was slowly added 10 (2.72 g, 10 mmol), and the resulting solution was stirred for 3 h at 23 "C before evaporation t o dryness. The residues were extracted with diethyl ether (15 mL) and then added to a wet THF solution (30 mL) of B a N F (4.70 g, 18 mmol). The mixture was stirred at 23 "C for 4 h, dried in vacuo, and finally chromatographed through a silica column to yield 13 as an orange solid (1.46 g, 3.5 mmol, 35%). (k)Synthesisof Methyl 7-Phenyl-7-hydroxy-2-methyl(E&)-2,4-heptadienate(14). To 7 (0.10 g, 0.23 mmol) in toluene (7 mL) was added benzaldehyde (50 mg, 0.67 mmol) at -60 "C and then BF3.Et20 (0.050 mL, 0.39 mmol). The mixture was stirred at -60 "C for 5 h to produce a red glassy solid. The toluene was decanted, and t o the red residue was added CHzCl2 (5 mL) at -60 "C. To this solution was added Me3NO (0.10 g, 1.30 mmol), and the mixture was stirred for 1 h at -60 "C before the temperature was raised t o 23 "C. After it was stirred for an additional 7 h, the solution was concentrated, and the residues were chromatographed through a preparative TLC plate to afford 14 as an oil (31 mg, 0.13 mmol, 56%): IR (Nujol, cm-') v(OH) 3422 (br, s), v(C=O) 1700 (s), v(C=C) 1638 (m); lH NMR (400 MHz, CDC13) 6 1.65 (s, 3H, Me), 2.59 (t, 2H, J = 7.2 Hz, CHzCHOH), 3.66 (8,3H, OMe), 4.72 (t, J = 6.2 Hz, l H , CHOH), 5.98 (dt, l H , J = 15.0, 7.2 Hz, =CHCHz), 6.38 (dd, l H , J=15.0, 11.5 Hz, =CH), 7.08 (d, l H , J = 11.5 Hz, CH=CMe), 7.27 (s, 5H, Ph); 13CNMR (100 MHz, CDC13) 6 12.6 (=CMe), 43.0 (CHzCHOH), 51.8 (OMe), 73.6 (CHOH), 126.1 (CCOZMe), 127.8 (=CHCHz), 137.7 (CH=CMe), 138.7 (=CH), 125.8 (Ph), 128.6 (Ph), 128.9 (Ph), 143.6 (Ph), 168.9 (C=O); HRMS calcd for C15H1803: 246.1256, found 246.1253. (1) Synthesis of Methyl 7-Hydroxy-2,8-dimethyl-(E&)2,4-nonadienate (15). This compound was similarly prepared from 7,isobutyraldehyde, and BFyEt20 in cold toluene according to the method described in section k;the yield of 15 was 50%: IR (neat, cm-l) v(OH) 3452 (br), v(C=O) 1703 (s), v(C=C) 1638 (m); lH NMR (400 MHz, CDC13) 6 0.90 (d, J = 5.1 Hz, 6H, CHMez), 1.64 (m, l H , CHMez), 1.67 (s, 3H, Me), 2.28 (m, 2H, =CHCHH'), 3.36 (dt, J = 6.2, 5.0 Hz, l H , CHOH), 3.69 (s, 3H, OCH3), 6.05 (dt, J = 15, 5.6 Hz, l H , =CHCHz), 6.38(dd,J=15.0,11.5Hz,1H,=CH-),7.12(d,J=11.2Hz, l H , CH=CMe); 13C NMR (100 MHz, CDC13) 6 12.6 (=CMe), 17.3 and 18.7 (CHMeZ), 33.2 (CHMez), 38.2 (=CHCHz), 51.8 (OMe), 75.8 (CHOH), 125.8 (CCOZMe), 128.2 (=CHI, 138.2 (CH=CMe), 139.0 (=CH), 169.0 (C=O); HRMS calcd for C12H2103 213.1490, found 213.1486. (m) Synthesis of Methyl 2-Methyl-9-oxo-2,4-decadienate (16). This compound was similarly prepared from 7, methyl vinyl ketone, and BFyEt20 in cold toluene according
2360 Organometallics, Vol. 14, No. 5, 1995
Liang et al.
Table 4. Crystal Data and Conditions for Crystallographic Data Collection and Structure Refinement for 3,6, and 13 6
formula FW diffractometer used space group
(A) (A) c (A) a b
(deg)
v (A31
z
Dc c ( g ~ m - 3 ) A(% F(OO0) unit cell detn: no. (28 range (deg)) scan type scan width (deg) scan speed (deg min-') 2Nmax) (deg) hkl ranges IA (cm-') cryst size (mm) transmissn temp (K) no. of meas rflns no. of obs rflns (I > 2.0dD) no. of unique f i n s RF;Rwu GOFb refinement program no. of atoms no. of refined params minimize function wt scheme wt modifier K (in KF>) g (2nd ext coeff) x lo4 Mu ( m a ) D-map ( m u ; min) (e/A3)
Nonius monoclinic, P2dn 7.759(3) 14.201(5) 12.638(3) 101.074(24) 1366.5(8) 4 2.091 0.7107 816 25 (18.60-32.44) 8/28 2(0.65 0.35 tan 8 ) 2.06-8.24 50.0 -9 to +9; 0-16; 0-15 86.399 0.40 x 0.50 x 0.60 0.340; 1.000 298.00 2390 2087 2390 0.032; 0.036 2.88 NRCVAX 33 193 (2087 out of 2390 rflns)
+
0.000 040
1.21(3) 0.077 -1.770; 1.810
to the method described in section k; the yield of 16 was 42%: IR (neat, cm-l) v(C=O) 1709 (s), v(C=C) 1639 (m), 1610 (m); 1H NMR (400 MHz, CDC13) 6 1.77 (m, 2H, CHZ),1.90 (s, 3H, =CMe), 2.10 (s, 3H, MeCO), 2.19 (m, 2H, CH2CH=), 2.46 (t, 2H, J = 5.0 Hz, CHzCO), 3.72 (s, 3H, OMe), 6.00 (dt, J = 15.4, 7.1 Hz, l H , =CH), 6.33 (dd, l H , J = 15.4,11.2 Hz, =CH), 7.15 (d, l H , J = 11.2Hz, CH=CMe); I3C NMR (100 MHz, CDC13) 6 12.5 (=CMe), 22.7 (MeCO), 30.0 and 32.3 (2 Me), 42.7 (CHzC=O), 51.8 (OMe), 125.8 (CCOZMe), 126.6 (=CHI, 138.4 HRMS calcd for (CH=), 141.7 (=CH), 169.1 (CO), 208.6 ((20); C12H1803 210.1256, found 210.1254. (n) Synthesis of Methyl 2-Methyl-9-oxo-2,4-undecadienate (17). This compound was similarly prepared from 7 , ethyl vinyl ketone, and BFyEt20 in cold toluene according to the method described in section k; the yield of 17 was 40%: IR (neat, cm-l) v(C=O) 1709 (s), v(C=C) 1639 (m), 1610 (m); lH NMR (400 MHz, CDC13) 6 1.77 (m, 2H, CHz), 1.90 (s, 3H, =CMe), 2.10 (s, 3H, MeCO), 2.19 (m, 2H, CHzCH=), 2.46 (t, 2H, J = 5.0 Hz,CHzCO), 3.72 (s, 3H, OC&), 6.00 (dt, J = 15.4, 7.1 Hz, l H , =CHCHz), 6.33 (dd, J = 15.4, 11.2 Hz, l H , =CH), 7.15 (d, J = 11.2 Hz, l H , =CH); I3C NMR (100 MHz, CDC13)6 12.5 (=CMe), 22.7 (MeC=O), 30.0 and 32.3 (2 CHd, 42.7 (CHzC=O), 51.8 (OMe), 125.8 (CCOzMe), 126.6 (=CHI,
3
13
Nonius orthorhombic, P212121 6.830(4) 11.862(4) 18.122(8)
Nonius orthorhombic, Pbca 8.066(5) 25.917(6) 18.618(4)
1468.1(12) 4 2.064 0.7107 892 25 (15.90-24.00) 13/28 2(0.80 0.35 tan 8) 2.06-8.24 50.0 0-8; 0-14; 0-21 80.508 0.05 x 0.10 x 0.35 0.914; 1.000 298.00 1503 1333 1503 0.032; 0.032 1.55 NRCVAX 37 191 (1333 out of 1503 rflns) C(wlF0 - FC19 l/u2(Fo) 0.000 070 2.67(25) 0.0508 -0.860; 1.560
3892(3) 8 1.844 0.7107 2056 25 (16.68-28.52) 8/28 2(0.75 + 0.35 tan 8) 2.06-8.24 45.0 0-8; 0-27; 0-20 60.885 0.30 x 0.40 x 0.45 0.439; 1.000 298.00 2541 1728 2541 0.032; 0.020 1.59 NRCVAX 40 253 (1728 out of 2541 rflns) C(wlF0 - Fc12) l/u2(Fo) 0
+
0
0.0119 -0.860; 1.010
138.4 (CH), 141.7 (=CH), 169.1 (CO), 208.6 (C=O); HRMS calcd for C13H20O3 224.1412, found 224.1413. X-ray Diffraction of 3,6,and 13. Single crystals of 3,6, and 13 were sealed in glass capillaries under an inert atomsphere. Data were collected on a Nonius CAD 4 using graphite-monochromatd Mo Ka radiation, and the structure was solved by the heavy-atom method; all data reduction and structure refinement were performed with the NRCCSDP package. Crystal data, details of the data collection, and the structure analysis are summarized in Table 4. For all structures, all non-hydrogen atoms were refined with anisotropic parameters, and all hydrogen atoms included in the structure factors were placed in idealized positions.
Acknowledgment. We wish to thank the National Science Council of the Republic of China for financial support of this work. Supplementary Material Available: Tables of atom coordinates, all bond distances and angles, and thermal parameters for 3,6,and 13 (9 pages). Ordering information is given on any current masthead page. OM950013Z
