Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 17, Issue 50, Pages 14199-14223Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201003383
Keywords
alkylation; allylic compounds; asymmetric catalysis; enolates; reaction mechanisms; synthetic methods
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Funding
- King Abdullah University of Science and Technology (KAUST) [KUS-11-006-02]
- NIH-NIGMS [R01 GM080269-01]
- Fannie and John Hertz Foundation
- Eli Lilly
- Ono Pharmaceutical Co., Ltd.
- Hungarian-American Enterprise Scholarship Fund
- Takeda Pharmaceutical Co., Ltd.
- University of California [14DT-0004]
- Marcella R. Bonsall and the Dalton Fund
- Caltech Amgen Scholars Program
- Ministry of Education, Culture, Sports, Science and Technology, Japan
- A. P. Sloan Foundation
- Research Corporation
- Dreyfus Foundation
- Bristol-Myers Squibb
- GlaxoSmithKline
- Johnson and Johnson
- Amgen
- Merck Research Laboratories
- Pfizer
- Novartis
- Roche
- Abbott Laboratories
- Boehringer-Ingelheim
- AstraZeneca
- Caltech
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alpha-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursor: enol carbonates, enol silanes, and racemic beta-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center.
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