Issue 35, 2021

Chirality memory of α-methylene-π-allyl iridium species

Abstract

Chirality is one of the most important types of steric information in nature. In addition to central chirality, axial chirality has been catching more and more attention from scientists. However, although much attention has recently been paid to the creation of axial chirality and the chirality transfer of allenes, no study has been disclosed as to the memory of such an axial chirality. The reason is very obvious: the chiral information is stored over three carbon atoms. Here, the first example of the memory of chirality (MOC) of allenes has been recorded, which was realized via an optically active alkylidene-π-allyl iridium intermediate, leading to a highly stereoselective electrophilic allenylation with amines. Specifically, we have established the transition metal-mediated highly stereoselective 2,3-allenylation of amines by using optically active 2,3-allenyl carbonates under the catalysis of a nonchiral iridium(III) complex. This method is compatible with sterically bulky and small substituents on both amines and 2,3-allenyl carbonates and furnishes the desired optically active products with a high efficiency of chirality transfer. Further mechanistic experiments reveal that the isomerization of the optically active alkylidene-π-allyl iridium intermediate is very slow.

Graphical abstract: Chirality memory of α-methylene-π-allyl iridium species

Supplementary files

Article information

Article type
Edge Article
Submitted
13 mai 2021
Accepted
20 jul 2021
First published
21 jul 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021,12, 11831-11838

Chirality memory of α-methylene-π-allyl iridium species

Y. Cui, Y. Zhai, J. Xiao, C. Li, W. Zheng, C. Huang, G. Wu, A. Qin, J. Lin, Q. Liu, H. Wang, P. Wu, H. Xu, Y. Zheng and S. Ma, Chem. Sci., 2021, 12, 11831 DOI: 10.1039/D1SC02636D

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