Synthesis of PdII complexes bearing an enantiomerically resolved seven-membered N-heterocyclic carbene ligand and initial studies of their use in asymmetric Wacker-type oxidative cyclization reactions

TETRAHEDRON

卷:65

Article

Scarborough, Christopher C.¹  Bergant, Ana¹  Sazama, Graham T.¹  Guzei, Ilia A.¹  Spencer, Lara C.¹  Stahl, Shannon S.¹ 

[1] Univ Wisconsin, Dept Chem, Madison, WI 53706 USA

关键词: N-Heterocyclic carbene;    Palladium;    Organometallic chemistry;    Wacker oxidation;   

DOI  :  10.1016/j.tet.2009.04.072

来源: Elsevier

【 摘 要 】

The development of enantiomerically resolved, axially-chiral seven-membered N-heterocyclic carbene ((NHC)-N-7) ligands for palladium is described. These (NHC)-N-7 ligands are derived from enatiomerically pure 2,2'-diamino-6,6'-dimethylbiphenyl, which is transformed via a synthetic sequence consisting of ortho-arylation, N-alkylation, and cyclization to afford seven-membered-ring amidinium salts. Synthesis of the seven-membered amidinium salts benefits from microwave irradiation, and in-situ metalation of the amidinium salts yields (NHC)-N-7-Pd-II complexes. The chiral (NHC)-N-7-Pd complexes were examined as chiral catalysts under aerobic conditions in two intramolecular oxidative amination reactions of alkenes. In one case, enantioselectivities up to 63% ee were obtained, while the other substrate underwent cyclization to afford essentially racemic products. The catalytic data compare favorably to results obtained with a Pd-II catalyst bearing a chiral five-membered-ring NHC ligand and, thereby, highlight the potential significance of this new class of chiral NHC ligands. (C) 2009 Elsevier Ltd. All rights reserved.

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