Enantioselective Rhodium-Catalyzed Allylic Alkylation of Prochiral α,α-Disubstituted Aldehyde Enolates for the Construction of Acyclic Quaternary Stereogenic Centers
- Resource Type
- Authors
- P. Andrew Evans; Timothy B. Wright
- Source
- Journal of the American Chemical Society. 138:15303-15306
- Subject
- chemistry.chemical_classification
010405 organic chemistry
Stereochemistry
Enantioselective synthesis
chemistry.chemical_element
General Chemistry
Alkylation
010402 general chemistry
01 natural sciences
Biochemistry
Aldehyde
Asymmetric induction
Catalysis
0104 chemical sciences
Rhodium
Stereocenter
Tsuji–Trost reaction
Colloid and Surface Chemistry
chemistry
- Language
- ISSN
- 1520-5126
0002-7863
A highly enantioselective rhodium-catalyzed allylic alkylation of prochiral α,α-disubstituted aldehyde enolates with allyl benzoate is described. This protocol provides a novel approach for the synthesis of acyclic quaternary carbon stereogenic centers and it represents the first example of the direct enantioselective alkylation of an aldehyde enolate per se. The versatility of the α-quaternary aldehyde products is demonstrated through their conversion to a variety of useful motifs applicable to target-directed synthesis. Finally, mechanistic studies indicate that high levels of asymmetric induction are achieved from a mixture of prochiral (E)- and (Z)-enolates, which provides an exciting development for this type of transformation.