Extended Enolates: Versatile Intermediates for Asymmetric C-H Functionalization via Noncovalent Catalysis

Catalyst-controlled functionalization of unmodified carbonyl compounds is a relevant operation in organic synthesis, especially when high levels of site- and stereo-selectivity can be attained. This objective is now within reach for some subsets of enolizable substrates using various types of activa...

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Bibliographic Details
Authors: Oyarbide Garmendia, Juan Miguel, Palomo Nicolau, Claudio
Format: article
Publication Date:2021
Country:España
Institution:Universidad del País Vasco
Repository:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/53267
Online Access:http://hdl.handle.net/10810/53267
Access Level:Open access
Keyword:asymmetric catalysis
Bronsted base catalysis
C-H functionalization
dienolates
regioselectivity
vinylogous michael addition
allylic-allylic alkylation
baylis-hillman carbonates
aldol reaction
3-alkylidene oxindoles
enantioselective addition
olefinic azlactones
mannich reaction
alpha
ketones
Description
Summary:Catalyst-controlled functionalization of unmodified carbonyl compounds is a relevant operation in organic synthesis, especially when high levels of site- and stereo-selectivity can be attained. This objective is now within reach for some subsets of enolizable substrates using various types of activation mechanisms. Recent contributions to this area include enantioselective transformations that proceed via transiently generated noncovalent di(tri)enolate-catalyst coordination species. While relatively easier to form than simple enolate congeners, di(tri)enolates are ambifunctional in nature and so control of the reaction regioselectivity becomes an issue. This Minireview discusses in some detail this and other problems, and how noncovalent activation approaches based on metallic and metal free catalysts have been developed to advance the field.