4.6 Article

Chiral Bis(imidazolidine)-Derived NCN Pincer Rh Complex for Catalytic Asymmetric Mannich Reaction of Malononitrile with N-Boc Imines

Journal

CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 30, Pages 10671-10675

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201502097

Keywords

asymmetric catalysis; malononitrile; pincer complexes; rhodium

Funding

  1. Ministry of Education, Culture, Sports, Science and Technology (Japan)
  2. Workshop on Chirality at Chiba University (WCCU)
  3. Grants-in-Aid for Scientific Research [26105706] Funding Source: KAKEN

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Chiral bis(imidazolidine)-derived NCN-rhodium complexes ([PhBidine-RhX2] and [tBu-PhBidine-RhX2]) were prepared by a CH insertion method, and the structures were unequivocally determined by X-ray crystallographic analysis. The [tBu-PhBidine-Rh(OAc)(2)] complex smoothly catalyzed an asymmetric Mannich reaction of malononitrile with N-Boc imines to give products in up to 94% ee, which are useful for the synthesis of chiral -amino acids.

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