Phosphine-Catalyzed Doubly Stereoconvergent γ-Additions of Racemic Heterocycles to Racemic Allenoates: The Catalytic Enantioselective Synthesis of Protected α,α-Disubstituted α-Amino Acid Derivatives

Journal of the American Chemical Society

Volumn 137, Issue 29, 2015, Pages 9438-9442

  Kalek, Marcin ^a   Fu, Gregory C ^a  

^a California Institute of Technology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBONYL COMPOUNDS; CATALYSIS; CHELATION; ENANTIOSELECTIVITY; NUCLEOPHILES; PHOSPHORUS COMPOUNDS; STEREOCHEMISTRY; STEREOSELECTIVITY; UNSATURATED COMPOUNDS;

ALPHA-AMINO ACIDS; CHEMICAL EQUATIONS; DIASTEREO-SELECTIVITY; ELECTROPHILES; ENANTIOSELECTIVE SYNTHESIS; HIGH STEREOSELECTIVITIES; STEREOGENIC CENTERS; UNSATURATED CARBONYL COMPOUNDS;

AMINO ACIDS;

AMINO ACID DERIVATIVE; ELECTROPHILE; HETEROCYCLIC COMPOUND; NUCLEOPHILE; PHOSPHINE DERIVATIVE; ALLENOLIC ACID; AMINO ACID; NAPHTHALENE DERIVATIVE; PHOSPHINE;

ADDITION REACTION; ARTICLE; CATALYSIS; CHIRALITY; ENANTIOSELECTIVITY; NUCLEOPHILICITY; STEREOCHEMISTRY; SYNTHESIS; CHEMISTRY; STEREOISOMERISM;

AMINO ACIDS; CATALYSIS; HETEROCYCLIC COMPOUNDS; NAPHTHALENES; PHOSPHINES; STEREOISOMERISM;

EID: 84938400328     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/jacs.5b05528     Document Type: Article

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30. We hypothesize that the phenol may serve as a proton shuttle in this process.
31. No kinetic resolution: References 3b, 3d.
32. Kinetic resolution: References 3c, 3e.
33. Estimated through computations: B3LYP/6-311+G(2d,2p); DFT-D3; CPCM; gas-phase G correction.
34. Under the same conditions but in the absence of the 1,3-oxazol-5(4H)-one, the allenoate isomerizes to the 1,3-diene (Reference 6) at a rate and with a selectivity factor (kinetic resolution of the allenoate) that are essentially identical to those for the γ-addition reaction, consistent with the two processes sharing the same turnover-limiting step (formation of A).