Catalytic discrimination between formyl groups in regio- and stereoselective intramolecular cross-aldol reactions
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 t...
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Published in | Chemical science (Cambridge) Vol. 7; no. 6; pp. 3791 - 3797 |
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Main Authors | , , , , , , |
Format | Journal Article |
Language | English |
Published |
CAMBRIDGE
Royal Soc Chemistry
01.01.2016
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Subjects | |
Online Access | Get full text |
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Summary: | 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. |
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Bibliography: | KAKEN ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 2041-6520 2041-6539 |
DOI: | 10.1039/c5sc04594k |