Development and application of asymmetric organocatalytic Mukaiyama and vinylogous Mukaiyama-type reactions

This is the peer reviewed version of the following article: "Development and application of asymmetric organocatalytic Mukaiyama and vinylogous Mukaiyama-type reactions", Chemistry - A European Journal 24.43 (2018): 10906-10933 ,which has been published in final form at https://doi.org/10.1002/chem.201801866. This article may be used for non-commercial purposes in accordance with Wiley terms and conditions for use of self-archived versionsOrganocatalysis is a growing area that is benefiting from advances in many fields. Its implementation has begun in areas such as supramolecular chemistry, organic chemistry and natural product synthesis. While a considerable number of important publications in the field of organocatalytic Mukaiyama-type additions have been reported, they are yet to be fully covered in a review. Therefore, we would like to highlight the applications of various kinds of organocatalysts in Mukaiyama-type reactions, while also including the vinylogous Mukaiyama variation. Herein we describe and discuss the development and current state of the art of the organocatalytic Mukaiyama reaction, vinylogous Mukaiyama and related reactionsFinancial support from the Spanish Government CTQ2015-64561-R (MINECO/FEDER) is gratefully acknowledged. M.F. thanks the UAM for an FPI-UAM fellowshi

Stereocontrolled Addition of Scrambling ortho-Sulfinyl Carbanions: Easy Access to Homopropargylamines and α-Allenylamines

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organic Letters, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see: https://pubs.acs.org/doi/abs/10.1021/acs.orglett.0c00625An unprecedented behavior of ortho-sulfinylpropargyl carbanions in the presence of optically active sulfinylimines affords two different families of compounds: this peculiar chemodivergency is importantly affected by the nature of the employed base, and assisted by the configuration of the electrophile, displaying no alteration in the stereocontrol of both reactions. α-Allenylamines are formed exclusively, using R-sulfinyl aldimines as electrophiles, while homopropargylamines result when S-sulfinyl aldimines are employed.We thank DGAPA-UNAM (Project No. PAPIIT-IN205319) for financial support. B.C.D. thanks CONACYT for a graduate fellowship (Grant No. 335839) and R.I.R. thanks Fundación Carolina for a graduate fellowship. We also thank M. C. García González, R. Gaviño, R. Patiño, M. A. Peña, and R. A. Toscano for their technical assistance (all from UNAM). We are grateful to the Spanish Government (No. RTI2018-095038-B-I00), “Comunidad de Madrid” and European Structural Funds (No. S2018/NMT-4367