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Pd‐catalyzed asymmetric allylic substitution reactions using P‐chirogenic diaminophosphine oxides: DIAPHOXs
Author(s) -
Nemoto Tetsuhiro,
Hamada Yasumasa
Publication year - 2007
Publication title -
the chemical record
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.61
H-Index - 78
eISSN - 1528-0691
pISSN - 1527-8999
DOI - 10.1002/tcr.20108
Subject(s) - allylic rearrangement , tsuji–trost reaction , stereocenter , amination , enantioselective synthesis , catalysis , chemistry , ligand (biochemistry) , substitution reaction , combinatorial chemistry , acetamide , medicinal chemistry , organic chemistry , receptor , biochemistry
This paper describes the development of a new class of chiral phosphorus ligand: aspartic acid‐derived P‐chirogenic diaminophosphine oxides, DIAPHOXs, and their application to several Pd‐catalyzed asymmetric allylic substitution reactions. Pd‐catalyzed asymmetric allylic alkylation was initially examined in detail using diaminophosphine oxides 1a , resulting in the highly enantioselective construction of quaternary stereocenters. Mechanistic investigations revealed that 1a is activated by N,O ‐bis(trimethylsilyl)acetamide‐induced tautomerization to afford a trivalent diamidophosphite species 12 , which functions as the actual ligand. Furthermore, asymmetric allylic amination was examined using Pd‐DIAPHOX catalyst systems, providing a variety of chiral allylic amines. © 2007 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 7: 150–158; 2007: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20108