Jump to main content
Jump to site search

Issue 6, 2017
Previous Article Next Article

A DFT calculation-inspired Rh(i)-catalyzed reaction via suppression of α-H shift in α-alkyldiazoacetates

Author affiliations

Abstract

Metal-associated carbenes from diazo compounds promote many useful chemistry transformations in modern organic chemistry. However, compared to α-aryldiazoacetate-derived carbenes (ArDCs), the synthetic application of α-alkyldiazoacetate-derived carbenes (AlDCs) is greatly limited due to intramolecular α-H transfer (elimination) that results in alkenes as the main by-products. An intriguing α-alkyldiazoacetate-involved three-component reaction has been developed following DFT calculation inspiration to provide β-hydroxyl α-alkyl-α-amino acid derivatives in good yields. The intramolecular α-H shift of an α-alkyldiazoacetate-derived carbene was successfully suppressed by the association of a Rh(I) complex to form the corresponding active ammonium ylide, which was trapped before the fast 1,2-H transfer process. A Rh(I)-chiral diene complex was identified as an effective catalyst to give an asymmetric version of the reaction with good enantioselectivity. This reaction provides insight into extending the efficient transformation of α-alkyldiazoacetate-derived carbenes and their synthetic application.

Graphical abstract: A DFT calculation-inspired Rh(i)-catalyzed reaction via suppression of α-H shift in α-alkyldiazoacetates

Back to tab navigation

Supplementary files

Article information


Submitted
18 Jan 2017
Accepted
21 Mar 2017
First published
22 Mar 2017

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2017,8, 4312-4317
Article type
Edge Article

A DFT calculation-inspired Rh(I)-catalyzed reaction via suppression of α-H shift in α-alkyldiazoacetates

S. Liu, J. Jiang, J. Chen, Q. Wei, W. Yao, F. Xia and W. Hu, Chem. Sci., 2017, 8, 4312
DOI: 10.1039/C7SC00257B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

Reproduced material should be attributed as follows:

  • For reproduction of material from NJC:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
  • For reproduction of material from PCCP:
    [Original citation] - Published by the PCCP Owner Societies.
  • For reproduction of material from PPS:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
  • For reproduction of material from all other RSC journals:
    [Original citation] - Published by The Royal Society of Chemistry.

Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.


Social activity

Search articles by author

Spotlight

Advertisements