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Recent Perspectives on Rearrangement Reactions of Ylides Via Carbene Transfer Reactions Sripati Jana, Yujing Guo, and Rene M

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Recent Perspectives on Rearrangement Reactions of Ylides Via Carbene Transfer Reactions Sripati Jana, Yujing Guo, and Rene M Minireview Chemistry—A European Journal doi.org/10.1002/chem.202002556 & Organic Chemistry |Reviews Showcase| Recent Perspectives on Rearrangement Reactions of Ylides via Carbene Transfer Reactions Sripati Jana, Yujing Guo, and Rene M. Koenigs*[a] Chem. Eur. J. 2020, 26,1–13 1 2020 The Authors. Published by Wiley-VCH GmbH && These are not the final page numbers! ÞÞ Minireview Chemistry—A European Journal doi.org/10.1002/chem.202002556 Abstract: Among the available methods to increase the mo- between p-bond and negatively charged atom followed by lecular complexity, sigmatropic rearrangements occupy a simultaneous redistribution of p-electrons. This minireview distinct position in organic synthesis. Despite being known describes the advances in this research area made in recent for over a century sigmatropic rearrangement reactions of years, which now opens up metal-catalyzed enantioselective ylides via carbene transfer reaction have only recently come sigmatropic rearrangement reactions, metal-free photo- of age. Most of the ylide mediated rearrangement processes chemical rearrangement reactions and novel reaction path- involve rupture of a s-bond and formation of a new bond ways that can be accessed via ylide intermediates. Introduction In 1912, Rainer Ludwig Claisen reported on the reaction of allyl vinyl ether 1a under thermal reaction conditions to deliver g,d-unsaturated carbonyl compound 2a, which is now text- book knowledge in undergraduate course and commonly known as the Claisen reaction (Scheme 1a).[1] The Claisen rear- rangement is an example of a [3,3]-sigmatropic rearrangement reaction. Sigmatropic rearrangement reactions are character- ized by the migration of a s-bond, flanked by at least one p- system, to a new position and the order of rearrangement re- actions is determined by the original and terminal position of the migratory group. Sigmatropic rearrangements thus involve the reorganization of multiple s-bonds and consequently enable the access of complex molecular systems through well- defined predictable transition states.[1] These features make sig- matropic rearrangement an important toolbox in synthesis methodology. This process can be classified into two key cate- gories (a) ylide mediated or neutral rearrangements (3 to 4) and (b) anionic or nonbonding electron pair mediated rear- rangements (5 to 6) (Scheme 1b,c).[2] Ylide mediated rearrangement reactions are accessed in general by two methods, either (a) by deprotonation of corre- sponding onium salts with a base or (b) by reaction of electro- Scheme 1. Rearrangement reactions. philic metal-carbene or free-carbene intermediates with a nu- cleophile.[2] The latter is one of the most important strategies to conduct efficient rearrangement reactions and the required proceeds, depending on the substituents pattern, via [2,3]- or electrophilic carbene intermediate, is most generally obtained [1,2]-sigmatropic rearrangement reactions (Scheme 2).[2] through metal-catalyzed or photochemical decomposition of The stereochemical configuration of the newly formed s- diazoalkanes 8. The reaction of the electron-deficient carbene bond can be controlled by the prevailing stereocenters within intermediate 8’ or 8’’ with a nonbonding lone pair of hetero- the starting materials, chiral ligands or chiral auxiliaries. These atom nucleophiles 7 generates a metal-bound ylide 10 or a strategies have been widely employed with limited success,[3,4] free ylide 9 that participates in the rearrangement step, which and only recently the first reports on highly enantioselective sigmatropic rearrangement reactions via carbene transfer reac- [5,6] [a] S. Jana, Y. Guo, Prof. Dr. R. M. Koenigs tions and ylide intermediate have been reported. The lack Institute of Organic Chemistry, RWTH Aachen University of existing methods and understanding can, in some part, be Landoltweg 1, 52074 Aachen (Germany) rationalized by missing knowledge on the rearrangement step E-mail: [email protected] Homepage: www.koenigslab.rwth-aachen.de itself. With the resurgence of photochemical carbene transfer The ORCID identification number(s) for the author(s) of this article can be reactions and detailed DFT calculations, the importance of free found under: https://doi.org/10.1002/chem.202002556. ylide intermediates in rearrangement was recently recog- 2020 The Authors. Published by Wiley-VCH GmbH. This is an open access nized.[7] article under the terms of Creative Commons Attribution NonCommercial An intricacy of ylide-mediated rearrangement reactions lies License, which permits use, distribution and reproduction in any medium, within the chemoselectivity of the rearrangement step itself provided the original work is properly cited and is not used for commercial purposes. and different types of rearrangement processes find common Selected by the Editorial Office for our Showcase of outstanding Review- application, depending on the substitution pattern of the ylide type articles http://www.chemeurj.org/showcase. intermediate (Scheme 2).[8–10] However, recent advances in this && Chem. Eur. J. 2020, 26,1–13 www.chemeurj.org 2 2020 The Authors. Published by Wiley-VCH GmbH ÝÝ These are not the final page numbers! Minireview Chemistry—A European Journal doi.org/10.1002/chem.202002556 research area now demonstrate initial application that permit face differentiation (formation of 25) and thus allows enantio- the control of the reaction pathway by choice of reaction con- specific ylide formation (Scheme 3b),[5,6] the other strategy har- ditions and therefore allow for new reactivity modes of ylide nesses latest developments in catalyst design to improve the intermediates.[11–14] face differentiation and thus allows for high asymmetric induc- This minireview aims at providing the reader with an over- tion.[6,23] view on the advances made in the past five years that have In 2017, Wang and co-workers reported on the first highly significantly developed the field of sigmatropic rearrangement enantioselective [2,3]-sigmatropic rearrangement reaction via carbene transfer reactions. These developments include the of allyl trifluoromethylsulfides 24. In the presence of the realization of highly enantioselective, metal-catalyzed sigma- Rh2(DOSP)4 catalyst, donor/acceptor diazoalkanes 7 readily un- tropic rearrangement reactions, metal-free photochemical rear- dergo formation of an electrophilic intermediate rhodium-car- rangement reactions and novel reaction pathways that can be bene complex 27, that can react with allyl trifluoromethylsul- accessed via ylide intermediates and that are not covered in fides 24 with a high degree of stereocontrol to form the pivo- previous reviews.[2] In each section, we will discuss the advan- tal ylide intermediate 25. Subsequent [2,3]-sigmatropic rear- ces that were made and give an overview on the respective re- rangement then furnishes the corresponding trifluoromethyl action mechanism to provide a detailed understanding. thioether 26 reaction products. Importantly, the stereo-deter- mining step lies within the addition reaction of the sulfide 24 Catalytic, Enantioselective Sigmatropic to the rhodium-carbene intermediate 27. The high degree of Rearrangements stereocontrol is presumably due to both steric and electronic Without doubt, asymmetric catalysis is one of the key advan- ces in the chemical sciences and was honored with the Nobel Prize in chemistry in 2001.[15] Many important milestones, rang- [16] Sripati Jana obtained his B.Sc. (2016) from ing from asymmetric organocatalysis, catalysis with chiral-at- RKMVC College Rahara, Kolkata, and M.Sc. [17] [18] metal complexes, or biocatalysis have been achieved and (2018) from Indian Institute of Technology today a plethora of different approaches towards catalytic, Kharagpur, India. In 2018, Sripati moved to asymmetric synthesis have been developed and revolutionized RWTH Aachen University, Germany, for his [19] doctoral study in the group of Prof. Dr. Rene modern synthesis. While asymmetric sigmatropic rearrange- M. Koenigs. His research interest is focused on ment reaction of allylic alcohols and derivatives thereof, have the metal catalyzed and photochemical car- been extensively studied by the Davies group and high levels bene transfer reactions. of enantioselectivity could be obtained,[20] the development of asymmetric sigmatropic rearrangement reactions proceeding via ylide intermediates of non-alcohol substrates remained elu- sive in organic synthesis. The [2,3]-sigmatropic rearrangement reaction of allyl sulfides Yujing Guo obtained her B.Sc. (2015) from 17 with diazoalkanes 8 was initially discovered in 1968 by Zhoukou Normal University, China, and M.Sc. Kirmse and Kapps, who reported on the copper-catalyzed reac- (2018) from Zhengzhou University, China. She tion of an allylic thiol with diazomethane.[21a] However, this re- then moved to RWTH Aachen University, Ger- many, for her doctoral study. She is working action only found its way into the organic synthesis repertoire in the group of Prof. Dr. Rene M. Koenigs after Doyle and co-workers rediscovered this transformation in since September 2018. He research interest is 1981.[21b] Since then, [2,3]-sigmatropic rearrangement of allyl focused on metal-catalyzed and photochemi- sulfides 17, or the Doyle–Kirmse reaction, has found wide- cal cyclopropanation reactions. spread application in organic synthesis to access highly func- tionalized building blocks with applications in total synthe- sis.[22] Many groups reported their efforts using chiral catalysts[3]
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