Catalytic Asymmetric Addition of Diorganozinc Reagents to N-Phosphinoylalkylimines

The synthesis of α-chiral amines bearing two alkyl groups has been hampered by the accessibility and stability of the alkylimine precursor. Herein, we report an efficient strategy to generate the alkyl-substituted imine in situ that is compatible with the MeDuPHOS monoxide·Cu(I) catalyzed addition o...

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Published inProceedings of the National Academy of Sciences - PNAS Vol. 101; no. 15; pp. 5405 - 5410
Main Authors Côté, Alexandre, Boezio, Alessandro A., Charette, André B., Halpern, Jack
Format Journal Article
LanguageEnglish
Published United States National Academy of Sciences 13.04.2004
National Acad Sciences
SeriesAsymmetric Catalysis Special Feature Part I
Subjects
Adducts
Aldehydes
Amides
Amines
Asymmetric Catalysis Special Feature Part I
Chemical compounds
Copper
Imines
Ligands
Organic chemistry
Physical Sciences
Reagents
Solvents
Sulfinic acids
Online AccessGet full text
ISSN0027-8424
1091-6490
DOI10.1073/pnas.0307096101

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Summary:The synthesis of α-chiral amines bearing two alkyl groups has been hampered by the accessibility and stability of the alkylimine precursor. Herein, we report an efficient strategy to generate the alkyl-substituted imine in situ that is compatible with the MeDuPHOS monoxide·Cu(I) catalyzed addition of diorganozinc reagents. The sulfinic acid adduct of the imine is readily prepared by mixing diphenylphosphinic amide, the aldehyde, and sulfinic acid. The sulfinic acid adduct is generally isolated by filtration. The addition of diorganozinc reagents in the presence of Me-DuPHOS monoxide·Cu(I) and the in situ-generated imines affords the corresponding α-chiral amines in high yields and enantiomeric excesses.
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Abbreviation: ee, enantiomeric excess.
To whom correspondence should be addressed. E-mail: andre.charette@umontreal.ca.
This paper was submitted directly (Track II) to the PNAS office.
Edited by Jack Halpern, University of Chicago, Chicago, IL, and approved February 4, 2004
ISSN:0027-8424
1091-6490
DOI:10.1073/pnas.0307096101