Palladium-Catalyzed Asymmetric Cycloaddition/Cope Rearrangement Relay: Synthesis of Chiral Endocyclic Allenes

Abstract

The synthesis of chiral endocyclic allenes, especially the medium-sized ones, remains a challenge in allene chemistry due to unfavorable tension and difficult stereocontrol. Herein, an efficient protocol for the construction of chiral nine-membered endocyclic allenes via palladium-catalyzed asymmetric cycloaddition/Cope rearrangement relay of vinyl carbonates with activated enynes is highlighted. This process provides rapid access to a variety of chiral nine-membered endocyclic allenes in good yields with excellent enantioselectivities. In particular, a chiral P,S-ligand shows good performance on stereoinduction, generating central and axial chirality in a single transformation, which is rationalized by DFT calculations and by a proposed transition state.

1 Introduction

2 Pd-Catalyzed Asymmetric Cycloaddition/Cope Rearrangement Relay

3 Plausible Mechanism and Stereochemical Outcome

4 Conclusion and Outlook

Key words

chiral allene - medium-sized ring - cycloaddition - Cope rearrangement - asymmetric catalysis

Publikationsverlauf

Eingereicht: 04. April 2023

Angenommen: 12. April 2023

Accepted Manuscript online:
12. April 2023

Artikel online veröffentlicht:
22. Mai 2023

• References

• 1 van t Hoff JH. La Chemie dans l’espace . Bazendijk; Rotterdam: 1875: 29
• 2 Alcaide B, Almendros P. Chem. Soc. Rev. 2014; 43: 2886
• 3a Krause N, Hashmi AS. K. Modern Allene Chemistry . Wiley-VCH; Weinheim: 2004
• 3b Liu L, Ward RM, Schomaker JM. Chem. Rev. 2019; 119: 12422
• 3c Alonso JM, Almendros P. Chem. Rev. 2021; 121: 4193
• 4 Hoffmann-Röder A, Krause N. Angew. Chem. Int. Ed. 2004; 43: 1196
• 5 Rivera-Fuentes P, Diederich F. Angew. Chem. Int. Ed. 2012; 51: 2818

For recent selected works, see:
• 6a Wang H.-N, Luo H.-W, Zhang Z.-M, Zheng W.-F, Yin Y, Qian H, Zhang J.-L, Ma S.-M. J. Am. Chem. Soc. 2020; 142: 9763
• 6b Law C.-Y, Kativhu E, Wang J, Morken JP. Angew. Chem. Int. Ed. 2020; 59: 10311
• 6c Zeng Y.-H, Chiou M.-F, Zhu X.-T, Cao J, Lv D.-Q, Jian W.-J, Li Y.-J, Zhang X.-H, Bao H.-L. J. Am. Chem. Soc. 2020; 142: 18014
• 6d Dong X.-Y, Zhan T.-Y, Jiang S.-P, Liu X.-D, Ye L, Li Z.-L, Gu Q.-S, Liu X.-Y. Angew. Chem. Int. Ed. 2021; 60: 2160
• 6e Yang L.-L, Ouyang J, Zou H.-N, Zhu S.-F, Zhou Q.-L. J. Am. Chem. Soc. 2021; 143: 6401
• 6f Zhang J.-C, Huo X.-H, Xiao J.-Z, Zhao L, Ma S.-M, Zhang W.-B. J. Am. Chem. Soc. 2021; 143: 12622

For recent examples:
• 7a Chu W.-D, Zhang L, Zhang Z.-K, Zhou Q, Mo F.-Y, Zhang Y, Wang J.-B. J. Am. Chem. Soc. 2016; 138: 14558
• 7b Trost BM, Zell D, Hohn C, Mata G, Maruniak A. Angew. Chem. Int. Ed. 2018; 57: 12916
• 7c He C.-Y, Tan Y.-X, Wang X, Ding R, Wang Y.-F, Wang F, Gao D.-D, Tian P, Lin G.-Q. Nat. Commun. 2020; 11: 4293
• 8 Johnson RP. Chem. Rev. 1989; 89: 1111
• 9 Daoust KJ, Hernandez SM, Konrad KM, Mackie ID, Winstanley JJr, Johnson RP. J. Org. Chem. 2006; 71: 5708
• 10a Marquis ET, Gardner PD. Tetrahedron Lett. 1966; 2793
• 10b Price JD, Johnson RP. Tetrahedron Lett. 1986; 27: 4679

For recent examples:
• 11a Barber JS, Styduhar ED, Pham HV, McMahon TC, Houk KN, Garg NK. J. Am. Chem. Soc. 2016; 138: 2512
• 11b Barber JS, Yamano MM, Ramirez M, Darzi ER, Knapp RR, Liu F, Houk KN, Garg NK. Nat. Chem. 2018; 10: 953
• 11c Yamano MM, Knapp RR, Ngamnithiporn A, Ramirez M, Houk KN, Stoltz BM, Garg NK. Angew. Chem. Int. Ed. 2019; 58: 5653
• 11d Kelleghan AV, Witkowski DC, McVeigh MS, Garg NK. J. Am. Chem. Soc. 2021; 143: 9338

For selected works, see:
• 12a Skattebøl L. Tetrahedron Lett. 1961; 167
• 12b Moore WR, Ward HR. J. Org. Chem. 1962; 27: 4179
• 12c Untch KG, Martin DJ, Castellucci NT. J. Org. Chem. 1965; 30: 3572
• 12d Ball WJ, Landor SR. J. Chem. Soc. 1962; 2298
• 12e Moore WR, Bertelson RC. J. Org. Chem. 1962; 27: 4182
• 13 Janßen CE, Krause N. Eur. J. Org. Chem. 2005; 2322

For selected works, see:
• 14a Brody MS, Williams RM, Finn MG. J. Am. Chem. Soc. 1997; 119: 3429
• 14b Kulyk S, Dougherty WG. Jr, Kassel WS, Fleming SA, Sieburth SM. Org. Lett. 2010; 12: 3296
• 14c Mömming CM, Kehr G, Wibbeling B, Fröhlich R, Schirmer B, Grimme S, Erker G. Angew. Chem. Int. Ed. 2010; 49: 2414

For selected works, see:
• 15a Sashida H, Tsuchiya T. Chem. Pharm. Bull. 1984; 32: 4600
• 15b Sashida H, Tsuchiya T. Chem. Pharm. Bull. 1986; 34: 3644
• 15c Perscheid M, Schollmeyer D, Nubbemeyer U. Eur. J. Org. Chem. 2011; 5250
• 15d Voskressensky LG, Titov AA, Dzhankaziev MS, Borisova TN, Kobzev MS, Dorovatovskii PV, Khrustalev VN, Aksenov AV, Varlamov AV. New J. Chem. 2017; 41: 1902
• 16 Zelder C, Krause N. Eur. J. Org. Chem. 2004; 3968
• 17a Ogasawara M, Okada A, Nakajima K, Takahashi T. Org. Lett. 2009; 11: 177
• 17b Ichio H, Murakami H, Chen Y, Takahashi T, Ogasawara M. J. Org. Chem. 2017; 82: 7503
• 18 Sweeney ZK, Salsman JL, Andersen RA, Berman RG. Angew. Chem. Int. Ed. 2000; 39: 2339
• 19 Zhang M.-M, Qu B.-L, Shi B, Xiao W.-J, Lu L.-Q. Chem. Soc. Rev. 2022; 51: 4146

For recent selected examples, see:
• 20a Yang L.-C, Wang Y.-N, Liu R.-Y, Luo Y.-X, Ng X.-Q, Yang B.-M, Rong Z.-Q, Lan Y, Shao Z.-H, Zhao Y. Nat. Chem. 2020; 12: 860
• 20b Trost BM, Zuo Z.-J. Angew. Chem. Int. Ed. 2020; 59: 1243
• 20c Liu Y.-Z, Wang Z.-A, Huang Z.-S, Zheng X, Yang W.-L, Deng WP. Angew. Chem. Int. Ed. 2020; 59: 1238
• 21a Wei Y, Lu L.-Q, Li T.-R, Feng B, Wang Q, Xiao W.-J, Alper H. Angew. Chem. Int. Ed. 2016; 55: 2200
• 21b Li M.-M, Wei Y, Liu J, Chen H.-W, Lu L.-Q, Xiao W.-J. J. Am. Chem. Soc. 2017; 139: 14707
• 21c Zhang Q.-L, Xiong Q, Li M.-M, Xiong W, Shi B, Lan Y, Lu L.-Q, Xiao W.-J. Angew. Chem. Int. Ed. 2020; 59: 14096
• 21d Li M.-M, Qu B.-L, Xiao Y.-Q, Xiao W.-J, Lu L.-Q. Sci. Bull. 2021; 66: 1719
• 21e Zhang M.-M, Chen P, Xiong W, Hui X.-S, Lu L.-Q, Xiao W.-J. CCS Chem. 2021; 4: 2620
• 21f Wang B.-C, Wei Y, Xiong F.-Y, Qu B.-L, Xiao W.-J, Lu L.-Q. Sci. China Chem. 2022; 65: 2347

For examples of nine-membered rings, see:
• 22a Mukai C, Ohta M, Yamashita H, Kitagaki S. J. Org. Chem. 2004; 69: 6867
• 22b Majhi TP, Neogi A, Ghosh S, Mukherjee AK, Helliwell M, Chattopadhyay P. Synthesis 2008; 94
• 22c Chinthapally K, Massaro NP, Sharma I. Org. Lett. 2016; 18: 6340
• 23a Ohnuma T, Hata N, Miyachi N, Wakamatsu T, Ban Y. Tetrahedron Lett. 1986; 27: 219
• 23b Gao X, Xia M.-R, Yuan C.-H, Zhou L.-J, Sun W, Li C, Wu B, Zhu D.-Y, Zhang C, Zheng B, Wang D.-Q, Guo H.-C. ACS Catal. 2019; 9: 1645
• 23c Wang Y, Cai P.-J, Yu Z.-X. J. Am. Chem. Soc. 2020; 142: 2777
• 24 CCDC 2122960 contains the supplementary crystallographic data for compound 4da. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures