Issue 6, 2016

Catalytic discrimination between formyl groups in regio- and stereoselective intramolecular cross-aldol reactions

Abstract

Catalytic discrimination between inequivalent formyl groups was achieved using an aniline-type acid–base catalyst for the regio-, diastereo-, and enantioselective intramolecular cross-aldol reactions of enolizable dials. Although L-proline gave a mixture of the regio- and stereoisomeric products in the presence of an N-containing 1,6-dial, the aniline-type catalyst afforded anti-3,4-disubstituted pyrrolidine in high regio-, and stereoselectivity beyond the background reaction, which led to the regioisomeric 2,3-disubstituted products. The mild reactivity of the aniline-type amine facilitated catalytic discrimination between the inequivalent formyl groups. Kinetic isotope effect studies and reductive amination experiments suggested that the regioselectivity was controlled under the enamine-forming steps.

Graphical abstract: Catalytic discrimination between formyl groups in regio- and stereoselective intramolecular cross-aldol reactions

Supplementary files

Article information

Article type
Edge Article
Submitted
29 Nov 2015
Accepted
18 Feb 2016
First published
22 Feb 2016
This article is Open Access

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

Chem. Sci., 2016,7, 3791-3797

Catalytic discrimination between formyl groups in regio- and stereoselective intramolecular cross-aldol reactions

T. Baba, J. Yamamoto, K. Hayashi, M. Sato, M. Yamanaka, T. Kawabata and T. Furuta, Chem. Sci., 2016, 7, 3791 DOI: 10.1039/C5SC04594K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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