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Asymmetric Rh(II)/Pd(0) Relay Catalysis: Synthesis of #Quaternary Chiral #-Lactams through Enantioselective CH Insertion/Diastereoselective Allylation of Diazoamides Liang-Zhu Huang, Zi Xuan, Hyun Ji Jeon, Zhen-Ting Du, Ju Hyun Kim, and Sang-gi Lee ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.8b01687 • Publication Date (Web): 29 Jun 2018 Downloaded from http://pubs.acs.org on June 29, 2018
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ACS Catalysis
Asymmetric Rh(II)/Pd(0) Relay Catalysis: Synthesis of -Quaternary Chiral β-Lactams through Enantioselective C-H Insertion/Diastereoselective Allylation of Diazoamides Liang-Zhu Huang,†,§† Zi Xuan, §† Hyun Ji Jeon,§ Zhen-Ting Du,†* Ju Hyun Kim‡* and Sang-gi Lee§* †
Shaanxi Key Laboratory of Natural Products and Chemical Biology School of Chemistry and Pharmacy, Northwest A&F University, Yangling 712100, Shannxi, P. R. China. ‡ Department of Chemistry (BK21 Plus), Research Institute of Natural Science, Gyeongsang National University, 52828, Jinju, Korea. § Department of Chemistry and Nano Science (BK21 Plus), Ewha Womans University, 120-750 Seoul, Korea. ABSTRACT: The straightforward route toward construction of α-quaternary chiral -lactam moiety via Rh(II)/Pd(0)-catalyzed stereoselective relay catalytic reaction is reported. This asymmetric dual relay catalysis involves Rh(II)-catalyzed enantioselective intramoluecular C-H insertions of α-diazoamides, and sequential Pd(0)-catalyzed diastereoselective intermolecular allylic alkylation. Under mild reaction conditions, a broad range of α-quaternary allylated chiral β-lactams have been synthesized in high yields (up to 99%) with excellent stereoselectivities (up to dr= >99:1, up to 98 % ee). KEYWORDS: -lactam, rhodium, palladium, C-H insertion, allylic alkylation, asymmetric catalysis
INTRODUCTION Asymmetric dual catalysis is a challenging yet ideal strategy in the synthesis of chiral compounds, as multiple bonds with numbers of stereogenic centers can be formed through stereoselective relay or cooperative reactions of distinct intermediates generated by simultaneous yet discrete catalytic events in a single reaction vessel.1 Beyond the rapid generation of molecular complexity and chirality, such methods are also attractive as lack of purification and/or isolation of the intermediates render them more sustainable with respect to pressing environmental concerns.2 Recent advances in asymmetric dual relay catalysis have been made mostly by combining a transition metal catalyst with organocatalysts such as amines, Brønsted acids, and N-heterocyclic carbenes.3 In contrast, the use of two-different transition metal catalysts in an asymmetric relay catalytic system have been far less explored,4 due in part to the difficulty in ensuring redox-compatibility between the metal catalysts, which is necessary to avoid catalyst deactivation. In addition, the mechanistic complexity and difficulty in achiving balanced kinetics between the catalyts restricted the widespread development of transition-metal-based asymmetric dual relay catalysis. Therefore, the design and implementation of transition-metalbased asymmetric dual relay catalytic system is a highly challenging subject. Herein, we disclose a novel asymmetric dual Rh(II)/Pd(0) relay catalysis to afford -quaternary allylated chiral -lactams in high yields (up to 99%) with excellent stereoselectivities (up to >99:1 dr; up to 98% ee) (Scheme 1b). β-Lactams are prevalent scaffolds in bioactive compounds such as well-known penicillin and cephalosporin derivatives,5 and thus the asymmetric catalytic reactions that could construct such four-membered chiral N-heterocyclic moiety are particu-
larly attractive.6 In this context, a number of efficient asymmetric catalytic methods have been developed to date including Rh(II)-catalyzed intramolecular C-H insertion of -diazo amides,7 Cu(I)-catalyzed cycloaddition of terminal alkynes with nitrones (asymmetric Kinugasa reaction),8 and [2+2] cycloadditions of imines with ketenes (Staudinger reactions).9
Scheme 1. Asymmetric relay catalysis for the synthesis of quaternary allylated chiral -lactams. Despite these advances, catalytic construction of the -lactam ring possessing -quaternary stereogenic center is quite limited.
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Hence, development of an efficient asymmetric catalytic reaction to afford the -quaternary chiral -lactam moiety is highly desirable. Although the examples are limited, Shintani and Fu could solve the inherent limitation of Kinugasa cyclization strategy (i.e., the direct construction of -quaternary chiral lactam ring is mechanistically not possible) through tandem relay catalysis, involving the Cu-catalyzed enantioselective intramolecular cycloaddition of 1-alkynes with nitrones, followed by diastereoselective allylic alkylation of the Cu-enolate intermediate (Scheme 1a).10 We recently reported a synergistic Rh(II)/Pd(0) dual catalytic strategy for the cross-coupling reaction between N-sulfonyl-1,2,3-triazoles and allylic substrates, in which redox-compatible Rh(II) and Pd(0) catalysts selectively activated triazoles and allylic substrates to generate 1,3ambivalent equivalent -imino Rh(II)-carbenoids and -allyl Pd(II)-complex intermediates, respectively, which were then reacted with each other in a chemo- and stereoselective manner.11 In the present work, we envisioned an asymmetric Rh(II)/Pd(0) dual relay catalysis through the combination of Rh(II)catalyzed intramolecular enantioselective C-H insertion of diazoamides with the Pd(0)-catalyzed intermolecular allylic alkylation to afford -quaternary allylated chiral -lactams. We anticipated that if Rh-carbenoids A, generated from -keto-dizoacetamide 1, undergo a rapid enantioselective C-H insertion reaction to first afford the chiral -lactams 4, a subsequent diastereoselective allylic alkylation could take place via the allyl Pd-complex B, which is generated in situ and in the same pot from allylic substrates 2 (Scheme 1b).
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the reaction did not proceeded at all, and most of the starting compounds were recovered (entries 6 and 7, Table 1). Table 1. Selected Examples for Reaction Optimization.a O
Ph
OBoc
+
N
(2.0 eq)
N2
Ph
1a
Rh(II)*
1d,e 2d,e 3d,e 4d,e 5d,e 6d,e 7d,e 8d,e 9f 10 11e 12 13 14 15 16 17,
Rh2[(S)-PTAD]4 Rh2[(S)-PTAD]4 Rh2[(S)-PTAD]4 Rh2[(S)-PTAD]4 Rh2[(S)-PTAD]4 Rh2[(S)-PTAD]4 Rh2[(S)-PTAD]4 Rh2[(S)-PTAD]4 Rh2[(S)-PTAD]4 Rh2[(S)-PTAD]4 Rh2[(R)-PTAD]4 Rh2[(S)-tert-PTTL]4 Rh2[(S)-PTTL]4 Rh2[(S)-PTPA]4 Rh2[(S)-NTTL]4 Rh2[(S)-DOSP]4 Rh2[(S)-BTPCP]4
O
N
Ph
Ligand
Yield(%) (dr)b
%eec
99 (85:15) 94 (78:22) 94 (85:15) 99 (87:13) 84 (91:9) 84 (90:10) 99 (88:12) 99 (86:14) 99 (91:9) 97 (89:11) 89 (91:9) 99 (88:12) -
90 88 89 84 85 80 94 -88 96 59 88 53 -
rac-BINAP Xantphos L1 L2 L3 dppp dppb dppf rac-BINAP rac-BINAP rac-BINAP rac-BINAP rac-BINAP rac-BINAP rac-BINAP rac-BINAP rac-BINAP O
R
N
O
3aa
O
It is well-documented that the regio-, chemo- and stereoselectivities in Rh(II)-catalyzed C-H insertion reaction of -diazo amides are highly dependent not only on the stereoelectronic property of the Rh(II) catalyst but also on the N-substituents.7,12 For example, the sterically bulky N-tert-butyl substituent may favour syn orientation to the sterically less demanding amide carbonyl group, providing a strong conformational bias for the facial cyclization.7d In addition, the tert-butoxide counter anion, generated in situ from the action of Pd(0) catalyst on allyl tertbutyl carbonate 2, may then act as a base to form the enolate required for the diastereoselective allylation of 4. This avoids the otherwise necessary introduction of a separate base for our reaction system. With these considerations in mind, the N-tertbutyl substituted -diazoamide 1a and allyl tert-butyl carbonate 2a were chosen as the model substrates for the optimization of one-pot asymmetric Rh(II)/Pd(0) relay catalysis. Preliminary data suggested that the reaction solvent significantly influenced the reactivity; and thus it was established that reactions in nonhalogenated and non-polar solvents such as n-hexane, cyclohexane, toluene, or mixtures thereof were superior to halogenated solvents like dichloroethane, dichloromethane, and chloroform (Table S1). The effects of phosphine ligands on Pd-catalysis were also investigated; however, the replacement of the BINAP with other bisphosphine ligands such as Xantphos and its analogous (L1-L3), dppp, dppb, and dppf did not improve the reaction efficiency (entries 2-8, Table 1). Interestingly, when the relay catalytic reaction was carried out using electronrich tBu-Xantphos (L1) ligand, only C-H insertion product 4a was formed in >95% yield (entry 3, Table 1). However, dppp and dppb ligands having conformationally flexible backbones,
O
Ph
2a
Entry
RESULTS AND DISCUSSIONS
[Rh] (1.0 mol %) Pd(dba)2 (2.0 mol %) Ligand (2.0 mol %) n-Hexane (0.05 M) 25 oC, 24 h
O
O O Rh Rh
R=
Rh2[(S)-PTAD]4
R=tert-Bu,
Rh2[(S)-PTTL]4
R=Bn,
Rh2[(S)-PTPA]4
Me
O
O Rh
O Rh
O Ph O
O O Rh Rh
Rh2[(S)-tert-PTTL]4
Ph
Ph2P
O Ph2P
PPh2 Xantphos
rac-BINAP
N
Me n
PPh2 PPh2
N
PPh2
n = 1: dppp n = 2: dppb
Rh2[(S)-NTTL]4
O
Rh
O
Rh
O
4
N Br Rh2([(S)-BTPCP]4
O O
Me
n
Rh
S O n-C12H25
Me
Rh
Rh2[(S)-DOSP]4
O (tBu)2P tBu-Xantphos
PPh2
O
4
P(tBu)2 (L1)
Ph2P
Fe PPh2
L2: n = 1 L3: n = 0
PPh2 dppf
[a]
Reaction conditions otherwise noted: 1a (0.1 mmol), 2a (0.2mmol) in the presence of Rh(II) (1.0 mol %), Pd (2.0 mol % based on Pd) and ligand (2.0 mol %) in n-hexane (2.0 mL) at 25 oC for 24 hours. [b]Determined by crude 1H NMR analysis (dimethoxyethane was used as an internal standard to determine the combined yield of major and minor diastereomers). [c]Determined by HPLC using chiral AD-H column. [d]In toluene/cyclohexane (v/v=1/1) solvent. [e]Pd2(dba)3 was used. [f][allylPdCl]2 was used.
When [allylPdCl]2 was used as a Pd precursor, the yield and enantioselectivity of the reaction were slightly depressed while diastereoselectivity was retained (entry 9, Table 1). When the Pd(0) precursor was changed to Pd(dba)2, the diastereoselectivity and enantioselectivity were slightly improved (compare entries 1 and 10, Table 1). The reactivity and enantioselectivity were retained when the reaction was conducted with enantiomeric Rh(II) catalyst, Rh2[(R)-PTAD]4, and afforded ent-3aa with 88 %ee, implying that the product stereochemistry can be determined by the chirality of the Rh catalyst (entry 11, Table 1). Next, the effects of Rh(II) catalyst on catalytic efficiency were examined (entries 12-17, Table 1). Among the Rh(II) catalysts investigated, the Rh2[(S)-tert-PTTL]4 exhibited best result, affording product 3aa in almost quantitative yield with 91:9 diastereomeric ratio and 96 %ee (entry 12, Table 1). The structure of 3aa could be determined unambiguously by X-ray
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ACS Catalysis structure analysis,13 in which the allyl and phenyl groups were installed in an trans-position, implying a sterically controlled allylation event of the enolate. However, the reaction efficiency was not improved by utilizing other Rh(II) catalysts such as Rh2[(S)-PTTL]4, Rh2[(S)-PTPA]4, Rh2[(S)-NTTL]4, Rh2[(S)DOSP]4, and Rh2[(S)-BTPCP]4 (entries 13-17, Table 1). As shown in path a in Scheme 2, when the -keto -diazo acetamides 1a (R = Ph) and 1b (R = CH3) were treated with Rh2[(S)-tert-PTTL]4 catalyst alone, the C-H insertion products trans-4a and trans-4b were formed in excellent yields with excellent diastereomeric ratio (dr = >99:1) and high enantioselectivities (4a: 94 %ee, 4b: 77 %ee). In contrast, the ester substituted diazo compound 1c afforded cis-4c in high yield of 89% with excellent diastereomeric ratio (dr >99:1) and enantioselectivity of 91 %ee. The trans/cis stereochemistry of these compounds was assigned based on the coupling constant of J3,4 = 2.1 Hz for trans-4a, trans-4b and J3,4 = 6.3 Hz for cis-4c. The absolute configurations were determined by comparison the sign of optical rotation with that of the reported ones, i.e., (3R,4R) for trans-4b {observed: []D25 = -14.8o (c = 0.23, CHCl3); reported: []D25 = -25.9 (c = 1.03, CHCl3)} and (3R, 4R) for cis-4c {observed: []D25 = +105.8 (c = 0.24, CHCl3); reported: []D25 = +84.5 (c = 2.02, CHCl3)}.7a,7d,14 When the isolated (3R,4R)-4a was subjected into the Pd-catalyzed allylic alkylation conditions, the -quaternary allylated -lactam 3aa was formed in 89% yields with dr = 80:20 and 90 %ee (path b in Scheme 2). This result clearly supported the reaction proceeded in a relay reaction with -lactam 4a as an intermediate. Interestingly, when the reaction was conducted in all-in-one-pot manner, the yield and stereoselectivity were increased to result in the -quaternary allylated -lactams 3aa, 3ba, and 3ca from 1a, 1b, and 1c, respectively. We next investigated the effects of allylic substrates on asymmetric dual relay catalytic reactions, and thus reacted 1a with 2 (X = OAc, OCO2Me, OCbz) (path c in Scheme 2). Interestingly, no allylated product 3aa was formed from the reaction with allyl acetate, but afforded only the C-H insertion adduct 4a in 62% yield with dr= >99:1. On the other hand, methyl (X = OCOOMe) or benzyl (X = OCbz) carbonates afforded 3aa as a major product. However, the reaction efficiencies in terms of yield, diastereoselectivity and enantioselectivity of 3aa were not higher than those from the reaction with 2a (X = OBoc), which may be attributable to the strong basicity of tert-BuO- counter anion facilitating formation of enolate from intermediate 4a for Pd-catalyzed allylic alkylation.
Scheme 2. Stepwise catalysis and one-pot relay catalysis for enantioselective synthesis of -quaternary allylated chiral lactams.
Table 2. Asymmetric Rh(II)/Pd(0) dual relay catalysis for one-pot synthesis of various -quaternary chiral -lactams.a R2 O
O
Ph
N N2
R
+
R2
OBoc
1
R
1
2
Rh2[(S)-tert-PTTL]4 (1.0 mol%) Pd(dba)2 (2.0 mol%) rac-BINAP (2.0 mol%) n-Hexane (0.05 M) 25 oC, 24 h
O O
Ph R1
N 3
R
[a] Reaction condition: 1 (0.1 mmol), 2a (0.2mmol) in the presence of Rh(II) (1.0 mol %), Pd(dba)2 (2.0 mol %), and racBINAP (2.0 mol %) in n-hexane (2.0 mL) at 25 oC for 24 hours. Yield is combined isolated yield of major and minor diastereomer which was separated, dr was determined by crude 1H NMR analysis, and % ee was determined by HPLC on a chiral stationary phase for the major diastereomer. [b]Xantphos (2.0 mol %) was used as a ligand.
While the optimized reaction conditions in hand (entry 12, Table 1), we next explored the generality of the asymmetric Rh/Pd dual relay catalysis (Table 2). As shown in Table 2A, the reactions of diverse array of N-benzyl α-diazoamides 1 bearing various electron-donating (1d-1h) and withdrawing groups (1i1q) on the different positions of the phenyl ring were carried out using allyl tert-butyl carbonate 2a. Both electron-donating methyl and methoxy groups and electron-withdrawing groups (-Br, -Cl, -F, -CF3, -NO2, -CN) at meta or para positions of the phenyl ring performed well under our reaction conditions and successfully provided the corresponding -quaternary allylated chiral β-lactams 3da-3qa with up to 99% yields in high diastereoselectivities (up to dr = 95:5) and enantioselectivities (up to 98 %ee). Noticeably, the reaction was affected by the position of substituents on the aromatic ring of R1 in which substituents with ortho-substituents showed low reactivity, giving poor to moderate yields and enantioselectivities in affording 3da (68%, 74 %ee) and 3na (54%, 62 %ee), which may attributable to increased steric hinderance. Pleasingly, the reactivities of -diazo amides having 1-naphthyl (1r) and heteroaromatic rings such as 2-furanyl (1s) and 2-thiophenyl (1t) afforded the corresponding chiral -lactams 3ra-3ta with excellent yields in good diastereoselectivities and moderate to excellent enantioselectivities. In addition, formation of four-membered -lactam 3ua from N-phenethyl substituted 1u strongly suggested that the C-H insertion reaction leads to the kinetically controlled product. When the N-tert-butyl group in 1a was replaced with
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benzyl (1v), the comparably good yield of product 3va was retained, but decreased distereoselectivity and enantioselectivity were observed (Table 2B). Finally, we varied the scope of allylic substrates, for which rac-BINAP ligand was replaced with Xantphos, giving higher yields (Table 2C). The asymmetric Rh(II)/Pd(0) dual relay catalytic reactions of 1a with various tert-butyl cinnamyl carbonates 2b-2j having different susbtituents on the phenyl ring could also smoothly undergo the desired transformations, and the corresponding -quaternary allylated chiral -lactams 3ab3aj were afforded in good yields and diastereomeric ratio with excellent enantioselectivities. The reactions using a tert-butyl cinnamyl carbonate 2b with the N-benzyl diazoamides1f, 1m, and 1o bearing electron-donating 4-methyl and electron-withdrawing 4-F and 4-CF3 substituent on the phenyl ring could also yield the corresponding -lactams (3fb, 3mb, and 3ob) in excellent yields with good diastereoselectivities and enatioselectivities. CONCLUSION We have developed a highly efficient novel asymmetric Rh(II)/Pd(0) dual relay catalysis for the one-pot synthesis of quaternary chiral -lactams, which promotes the sequential enantioselective intramolecular C-H insertion reaction of Rh(II)carbenoids derived from -diazo acetamides, followed by diastereoselective Pd-catalyzed allyl alkylation of -allyl Pd-complex, generated from allyl carbonates. This asymmetric dual relay catalysis process proceeds in a regio- and stereoselective manner to afford chiral -lactams with excellent enantioselectivities. Given the widespread availability of the diazo compounds and allyl carbonates, this asymmetric dual relay catalysis strategy may be a cornerstone for many new reactions exploiting multi-metallic transformations of Rh(II)-carbenoids and -allyl Pd(II)-complexes. Further studies along this line are underway in our laboratory. Corresponding Author *Email:
[email protected]. *Email:
[email protected]. *Email:
[email protected].
ORCID Sang-gi Lee: 0000-0003-2565-5233 Ju Hyun Kim: 0000-0003-4587-7714 Zhen-Ting Du: 0000-0001-5472-9815
Author Contributions †These
authors are equally contributed to this work. All authors have given approval to the final version of the manuscript.
Notes The authors declare no competing financial interest.
Supporting Information. Details of the experimental procedures, characterization data, copies of 1H and 13C NMR spectra of products (PDF), X-ray data for 3aa, and copies of HPLC chromatograpy for optical purity of products. This material is available free of charge via the internet at http://pubs.acs.org.
ACKNOWLEDGMENT
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This work was made possible through the financial support by the Samsung Science and Technology Foundation (SSTF-BA1401-10). We thank Dr Y. Kim for X-ray analysis and Dr. U. Kim for critical reading of this manuscript at NanoBio Institute in Ewha Womans University.
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ACS Catalysis Electrophiles via Cooperative Catalysis: The Direct Asymmetric α‑Allylation of Aryl Acetic Acid Esters. J. Am. Chem. Soc. 2016, 138, 5214-5217. (h) Zhao, F.; Li, N.; Zhu, Y.-F.; Han, Z.-Y. Enantioselective Construction of Functionalized Tetrahydrocarbazoles Enabled by Asymmetric Relay Catalysis of Gold Complex and Chiral Brønsted Acid. Org. Lett. 2016, 18, 1506-1509. (i) Afewerki, S.; Ma, G.; Ibrahem, I.; Liu, L.; Sun, J.; Córdova, A. Highly Enantioselective Control of Dynamic Cascade Transformations by Dual Catalysis: Asymmetric Synthesis of Polysubstituted Spirocyclic Oxindoles. ACS Catal. 2015, 5, 1266-1272. (j) Lu, L.-Q.; Li, Y.; Junge, K.; Beller, M. Relay Iron/Chiral Brønsted Acid Catalysis: Enantioselective Hydroge-nation of Benzoxazinones. J. Am. Chem. Soc. 2015, 137, 2763-2768. (k) Suzuki, T.; Ismiyarto.; Ishizaka, Y.; Zhou, D.-Y.; Asano, K.; Sasai, H. One-Pot Catalysis Using a Chiral Iridium Complex/Brønsted Base: Catalytic Asymmetric Synthesis of Catalponol. Org. Lett. 2015, 17, 5176-5179. (4) Selected papers on asymmetric relay dual metal catalysis, see: (a) Zhang, Z.-F.; Zhu, D.-X.; Chen, W.-W.; Xu, B.; Xu, M.-H. Enantioselective Synthesis of gem-Diaryl Benzofuran-3(2H)‑ones via One-Pot Asymmetric Rhodium/Palladium Relay Catalysis. Org. Lett. 2017, 19, 2726-2729. (b) Li, J.; Lin, L.; Hu, B.; Zhou, P.; Huang, T.;Liu, X.;Feng, X. Gold(I)/Chiral N,N’-Dioxide–Nickel(II) Relay Catalysis for Asymmetric Tandem Intermolecular Hydroalkoxylation/Claisen Rearrangement. Angew. Chem. Int. Ed. 2017, 56, 885-888. (c) Li, J.; Lin, L.; Hu, B.; Lian, X.; Wang, G.; Liu, X.; Feng, X. Bimetallic Gold(I)/Chiral N,N’-Dioxide Nickel(II) Asymmetric Relay Catalysis: Chemo- and Enantioselective Synthesis of Spiroketals and Spiroaminals. Angew. Chem. Int. Ed. 2016, 55, 6075-6078. (d) Dhiman, S.; Mishra, U. K.; Ramasastry, S. S. V. One-Pot Trimetallic Relay Catalysis: A Unified Approach for the Synthesis of -Carbolines and Other [c]-Fused Pyridines. Angew. Chem. Int. Ed. 2016, 55, 7737-7741. (e) Zhang, L.; Qureshi, Z.; Sonaglia, L.; Lautens, M. Sequential Rhodium/Palladium Catalysis: Enantioselective Formation of Dihydroquinolinones in the Presence of Achiral and Chiral Ligands. Angew. Chem. Int. Ed. 2014, 53, 13850-13853. (f) Nahra, F.; Macé, Y.; Lambin, D.; Riant, O. Copper/Palladium-Catalyzed 1,4 Reduction and Asymmetric Allylic Alkylation of ,β-Unsaturated Ketones: Enantioselective Dual Catalysis. Angew. Chem. Int. Ed. 2013, 52, 3208-3212. (g) Wang, Y.; Liu, L.; Zhang, L. Combining Zn ion catalysis with homogeneous gold catalysis: an efficient annulation approach to N-protected indoles. Chem. Sci. 2013, 4, 739-746. (h) Friedman, A. A.; Panteleev, J.; Tsoung, J.; Huynh, V.; Lautens, M. Rh/Pd Catalysis with Chiral and Achiral Ligands: Domino Synthesis of AzaDihydrodibenzoxepines. Angew. Chem. Int. Ed. 2013, 52, 9755-9758. (i) Ikeda, M.; Miyake, Y.; Nishibayashi, Y. Cooperative Catalytic Reactions Using Distinct Transition-Metal Catalysts: Ruthenium- and Copper-Catalyzed Enantioselective Propargylic Alkylation. Chem. Eur. J. 2012, 18, 3321-3328. (j) Corkey, B. K.; Toste, F. D. Catalytic Enantioselective Conia-Ene Reaction. J. Am. Chem. Soc. 2005, 127, 17168-17169. (5) Selected reviews, see: : (a) Tahlan, K.; Jesen, S. E. J. Origins of the β-lactam rings in natural products. Antibiot. 2013, 66, 401-410. (b) Böttcher, T.; Sieber, S. A. β-Lactams and β-lactones as activity-based probes in chemical biology. Med. Chem. Commun. 2012, 3, 408-417. (c) Bari, S. S.; Bhalla, A. Spirocyclic β-Lactams: Synthesis and Biological Evaluation of Novel Heterocycles. Top. Het. Chem. 2010, 22, 49-99. (d) Palomo, C.; Aizpurua, J. m. Ganboa, I.; Oiarbide, M. Asymmetric Synthesis of β‑Lactams by Staudinger Ketene‐Imine Cycloaddition Reaction. Eur. J. Org. Chem. 1999, 3223-3235. (6) Selected recent papers, see: (a) Xu, J.; Yuan, S.; Peng, J.; Miao, M.; Chen, Z.; Ren, H. Enantioselective [2+2] Annulation of Simple Aldehydes with Isatin Derived Ketimines via Oxidative N-Heterocyclic Carbene Catalysis. Chem. Commun. 2017, 53, 3430-3433. (b) Dailler, D.; Rocaboy, R.; Baudoin, O. Synthesis of β-Lactams by Palladium(0)Catalyzed C(sp3)-H Carbamoylation. Angew. Chem. Int. Ed. 2017, 56, 7218-7222. (c) Chauhan, P.; Mahajan, S.; Kaya, U.; Valkonen, A.; Rissanen, K.; Enders, D. Asymmetric Synthesis of Spiro β-Lactams via a Squaramide Catalyzed Sulfa-Michael Addition/Desymmetrization Protocol. Adv. Synth. Catal. 2016, 358, 3173-3178. (d) Pitts, C. R.; Lectka, T. Chemical Synthesis of β-Lactams: Asymmetric Catalysis and Other
Recent Advances. Chem. Rev. 2014, 114, 7930-7953. (e) Pedroni, J.; Boghi, M.; Saget, T.; Cramer, N. Access to β-Lactams by Enantioselective Palladium(0)-Catalyzed C(sp3)-H Alkylation. Angew. Chem. Int. Ed. 2014, 53, 9064-9067. (f) Magriotis, P. A. Progress in Asymmetric Organocatalytic Synthesis of β-Lactams. Eur. J. Chem. 2014, 26472657. (g) He, M.; Bode, J. W. Enantioselective, NHC-Catalyzed Bicyclo-β-Lactam Formation via Direct Annulations of Enals and Unsaturated N-Sulfonyl Ketimines. J. Am. Chem. Soc. 2008, 130, 418-419. (h) Li, G. -Q.; Li, Y.; Dai, L. –X.; You, S. –L. Enantioselective Synthesis of cis-4-Formyl-β-lactams via Chiral N-Heterocyclic Carbene-Catalyzed Kinetic Resolution. Adv. Synth. Catal. 2008, 350, 1258-1262. (i) Chowdari, N. S.; Suri, J. T.; Barbas III, C. F. Asymmetric Synthesis of Quaternary - and β-Amino Acids and β-Lactams via Proline-Catalyzed Mannich Reactions with Branched Aldehyde Donors. Org. Lett. 2004, 6, 2507-2510. (j) Natarajan, A.; Wang, K.; Ramamurthy, V.; Scheffer, J. R.; Patrick, B. Control of Enantioselectivity in the Photochemical Conversion of -Oxoamides into β-Lactam Derivatives. Org. Lett. 2002, 4, 1443-1446. (k) Magriotis, P. A. Recent Progress in the Enantioselective Synthesis of β-Lactams: Development of the First Catalytic Approaches. Angew. Chem. Int. Ed. 2001, 40, 4377-4379. (7) Selected papers, see: (a) Xu, X.; Deng, Y.; Yim, D. N.; Zavalij, P. Y.; Doyle, M. P. Enatioselective cis-β-lactam synthesis by intramolecular C-H functionalization from enoldiazoacetamides and derivative donor-acceptor cyclopropenes. Chem. Sci. 2015, 6, 2196-2201. (b) Candeias, N. R.; Carias, C.; Gomes, L. F. R.; André, V.; Duarte, M. T.; Gois, P. M. P.; Afonso, C. A. M. Asymmetric Intramolecular C-H insertion of a-Diazoacetamides in Water by Dirhodium(II) Catalysts Derived from Natural Amino Acid. Adv. Synth. Catal. 2012, 354, 29212927. (c) Anada, M.; Watanabe, N.; Hashimoto, S. Highly enantioselective construction of the key azetidin-2-ones for the synthesis of carbapenem antibiotics via intramolecular C–H insertion reactions of αmethoxycarbonyl-α-diazoacetamides catalysed by chiral dirhodium(II) carboxylates. Chem. Commun. 1998, 1517-1518. (d) Doyle, M. P.; Kalinin, A. V. Highly Enantioselective Route to β-Lactams via Intramolecular C-H Insertion Reactions of Diazoacetyl-azacycloalkanes Catalyzed by Chiral Dirhodium(II) Carboxamidates. Synlett. 1995, 10751076. (e) Watanabe, N.; Anada, M.; Hashimoto, S.; Ikegami, S. Enantioselective Intramolecular C-H insertion Reactions of N-Alkyl-N-tertButyl--Methoxycarbonyl--Diazoacetamides Catalyzed by Dirhodium(II) Carboxylates: Catalytic, Asymmetric Constriction of 2-Azetidinones. Synlett. 1994, 1031-1033. (f) Doyle, M. P.; Protopopova, M. N.; Winchester, W. R.; Daniel, K. L. Enantiocontrol and Regiocontorol in Lactam Syntheses by Intramolecular Carbon-Hydrogen Insertion Reactions of Diazoacetamides Catalyzed by Chiral Rhodium(II) Carboxamides. Tetrahedron Lett. 1992, 33, 7819-7822. (g) McCarthy, N.; McKervey, M. A.; Ye, T. A New Rhodium(II) Phosphate Catalyst for Diazocarbonyl Reactions Including Asymmetric Synthesis. Tetrahedron Lett. 1992, 33, 5983-5986. (8) (a) Wolosewicz, K.; Michalak, M.; Adamek, J.; Furman, B. Studies on the Enantioselective Kinugasa Reaction: Efficient Synthesis of β-Lactams Catalyzed by N-PINAP/CuX Complexes. Eur. J. Org. Chem. 2016, 2212-2219. (b) Alcaide, B.; Almendros, P.; Luna, A. Novel achievements with an old metal: copper-promoted synthesis of four-membered azacycles. RSC Adv. 2014, 4, 1689-1707. (c) Baeza, B.; Casarrubios, L.; Sierra, M. A. Towards a General Synthesis of 3-MetalSubstituted β-Lactams. Chem. Eur. J. 2013, 19, 11536-11540. (d) Chen, Z.; Lin, L.; Wang, M.; Liu, X.; Feng, X. Asymmetric Synthesis of trans-β-Lactams by a Kinugasa Reaction on Water. Chem. Eur. J. 2013, 19, 7561-7567. (e) Coyne, A. G.; Müller-Bunz, H.; Guiry, P. J. The asymmetric synthesis of β-lactams: HETPHOX/Cu(I) mediated synthesis via the Kinugasa reaction. Tetrahedron: Aymmetry. 2007, 18, 199-207. (f) Ye, M. –C.; Zhou, J.; Tang, Y. Trisoxazoline/Cu(II)Promoted Kinugasa Reaction. Enantioselective Synthesis of β-Lactams. J. Org. Chem. 2006, 71, 3576-3582. (g) Marco-Contelles, J. β-Lactam Synthesis by the Kinugasa Reaction. Angew. Chem., Int. Ed. 2004, 43, 2198−2200. (h) Lo, M. M. –C.; Fu, G. C. Cu(I)/Bis(azaferrocene)-Catalyzed Enantioselective Synthesis of β-Lactams via Couplings of Alkynes with Nitrones. J. Am. Chem. Soc. 2002, 124, 4572-4573. (i) Miura, M.; Enna, M.; Okuro, K.; Nomura, M. Copper-Catalyzed Reaction of Terminal Alkynes with Nitrones. Selective Synthesis of 1-ha-1-
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buten-3-yne and 2-hetidinone Derivatives. J. Org. Chem. 1995, 60, 4999-5004. (9) -Quaternary chiral -lactams have been synthesized by asymmetric[2+2] cycloaddition between disubstituted ketenes and imines, see: (a) Chen, S.; Salo, E. C.; Wheeler, K. A.; Kerrigan, N. J. BINAPHANE-Catalyzed Asymmetric Synthesis of trans-β-Lactams from Disubstituted Ketenes and N-Tosyl Arylimines. Org. Lett. 2012, 14, 1784-1787. (b) Zhang, Y.-R.; He, L.; Shao, P.-L.; Ye, S. Chiral N-Heterocyclic Carbene Catalyzed Staudinger Reaction of Ketenes with Imines: Highly Enantioselective Synthesis of N-Boc β-Lactams. Org. Lett. 2008, 10, 277-280. (c) Berlin, J. M.; Fu, G. C. Enantioselective Nucleophilic Catalysis: The Synthesis of Aza-β-Lactams through [2+2] Cycloadditions of Ketenes with Azo Compounds. Angew. Chem. Int. Ed. 2008, 47, 7048-7050. (d) Hodous, B. L.; Fu, G. C. Enantioselective Staudinger Synthesis of β-Lactams Catalyzed by a Planar-Chiral Nucleophile. J. Am. Chem. Soc. 2002, 124, 1578-1579. (10) Shintani, R.; Fu, G. C. Catalytic Enantioselective Synthesis of β-Lactams: Intramolecular Kinugasa Reactions and Interception of an Intermediate in the Reaction Cascade. Angew. Chem. Int. Ed. 2003, 42, 4082-4085. (11) Chen, Z.-S.; Huang, L.-Z.; Jeon, H. J.; Xuan, Z.; Lee, S.-g. Cooperative Pd(0)/Rh(II) Dual Catalysis: Interceptive Capturing of π‑Allyl Pd(II) Complexes with α‑Imino Rh(II) Carbenoids. ACS Catal. 2016, 6, 4914-4919. (12) (a) Candeias, N. P.; Gois, P. M. P.; Afonso, C. A. M. Rh(II)Catalyzed Intramolecular C-H Insertion of Diazo Substrates in Water: Scope and Limitations. J. Org. Chem. 2006, 71, 5489-5497. (b) Choi, M. K.-W.; Yu, W.-Y.; Che, C.-M. Ruthenium-Catalyzed Stereoselective Intramolecular Carbenoid C-H Insertion for β- and γ-Lactam Formations by Decomposition of α-Diazoacetamides. Org. Lett. 2005, 7, 1081-1084. (c) Gois, P. M. P.; Afonso, G. A. M. Regio- and Stereoselective Dirhodium(II)-Catalysed Intramolecular C-H Insertion Reactions of α-Diazo-α-(dialkoxyphosphoryl)acetamides and -acetates. Eur. J. Org. Chem. 2003, 3798-3810. (d) Doyle, M. P.; Forbes, D. C. Recent Advances in Asymmetric Catalytic Metal Carbene Transformations. Chem. Rev. 1998, 98, 911-925. (13) For X-ray structure data of 3aa (CCDC 1579004), see the Supporting Information. (14) (a) He, W.; Zhuang, J.; Yang, Z.; Xu, J. Sterically controlled diastereoselectivity in thio-Staudinger cycloadditions of alkyl/alkenyl/aryl-substituted thioketenes. Org. Biomol. Chem. 2017, 15, 5541-5548. (b) Vaske, Y. S. M.; Mahoney, M. E.; Konopelski, J. P.; Rogow, D. L.; McDonald, W. J. Enantiomerically Pure trans--Lactams from -Amino Acids via Compact Fluorescent Light (CFL) Continuous-Flow Photolysis. J. Am. Chem. Soc. 2010, 132, 11379-11385. (c) Bhalla, A.; Madan, S.; Venugopalam, P.; Bari, S. S. C-3 β-lactam carbocation equivalents: versatile synthons for C-3 substituted β-lactams. Tetrahedron. 2006, 62, 5054-5063. (d) Bennardi, L.; Bonini, B. F.; Comes-Franchini, M.; Dessole, G.; Fochi, M.; Ricci, A. One-Pot Synthesis of Novel Enantiomerically Pure and Racemic 4-Ferrocenyl-lactams and Their Reactivity in Acidic Media. Eur. J. Org. Chem. 2005, 3326-3333.
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