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Palladium(0) π-Lewis Base Catalysis: Concept and Development
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DOI：10.1021/jacs.3c14674.png)
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Abstract
En 中文
The development of a new catalytic strategy plays a vital role in modern organic chemistry since it permits bond formation in an unprecedented and more efficient manner. Although the application of preformed metal complexes as pi-base-activated reagents have enabled diverse transformations elegantly, the concept and strategy by directly utilizing transition metals as efficient pi-Lewis base catalysts remain underdeveloped, especially in the field of asymmetric catalysis. Here, we outline our perspective on the discovery of palladium(0) as an efficient pi-Lewis base catalyst, which is capable of increasing the highest occupied molecular orbital (HOMO) energy of both electron-neutral and electron-deficient 1,3-dienes and 1,3-enynes upon flexible eta(2)-complexes formed in situ and resultant pi-backdonation. Thus, fruitful carbon-carbon-forming reactions with diverse electrophiles can be achieved enantioselectively in a vinylogous addition pattern, which is conceptually different from the classical oxidative cyclization mechanism. Emphasis will be given to the concept and mechanism elucidation, catalytic features, and reaction design together with perspective on the further development of this emerging field.
Keywords:
AUTO-TANDEM CATALYSIS
ALKYLATIVE CYCLIZATION
ALDEHYDES
1,3-ENYNES
ANNULATION
COMPLEXES
MECHANISM
ACIDS
CONSTRUCTION
ISOTHIOUREAS
Journal
IF:
15.6
Papers:
20.0W
Citations:
60.2W