Catalytic asymmetric Mannich-type reaction of N-alkylidene-α-aminoacetonitrile with ketimines

Shaoquan Lin, Yuji Kawato, Naoya Kumagai, Masakatsu Shibasaki

Research output: Contribution to journalArticlepeer-review

34 Citations (Scopus)

Abstract

Optically active vicinal diamines are versatile chiral building blocks in organic synthesis. A soft Lewis acid/hard Brønsted base cooperative catalyst allows for an efficient stereoselective coupling of N-alkylidene-α-aminoacetonitrile and ketimines to access this class of compounds bearing consecutive tetra- and trisubstituted stereogenic centers. The strategic use of a soft Lewis basic thiophosphinoyl group for ketimines is the key to promoting the reaction, and aliphatic ketimines serve as suitable substrates with as little as 3 mol % catalyst loading. Getting in key: A soft Lewis acid/hard Brønsted base cooperative catalyst allows for efficient stereoselectives coupling of N-alkylidene-α-aminoacetonitrile and aliphatic ketimines to access vicinal diamines bearing consecutive tetra- and trisubstituted stereogenic centers. The use of a soft Lewis basic thiophosphinoyl group on the ketimines is key to promoting the reaction with as little as 3 mol % catalyst loading.

Original languageEnglish
Pages (from-to)5183-5186
Number of pages4
JournalAngewandte Chemie - International Edition
Volume54
Issue number17
DOIs
Publication statusPublished - 2015 Apr 20
Externally publishedYes

Keywords

  • asymmetric catalysis
  • copper
  • ketimines
  • Mannich reaction
  • nitriles

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Fingerprint

Dive into the research topics of 'Catalytic asymmetric Mannich-type reaction of N-alkylidene-α-aminoacetonitrile with ketimines'. Together they form a unique fingerprint.

Cite this