3-Azabicyclo[3.1.0]hex-1-ylamines by Ti-Mediated Intramolecular Reductive Cyclopropanation of α-(N-Allylamino)-Substituted N,N-Dialkylcarboxamides and Carbonitriles

✍ Scribed by Martina Gensini; Sergei I. Kozhushkov; Dmitrii S. Yufit; Judith A. K. Howard; Mazen Es-Sayed; Armin de Meijere

• Publisher: John Wiley and Sons
• Year: 2002
• Tongue: English
• Weight: 217 KB
• Volume: 2002
• Category: Article
• ISSN: 1434-193X
• DOI: 10.1002/1099-0690(200208)2002:15<2499::aid-ejoc2499>3.0.co;2-v

✦ Synopsis

A variety of tris-and monoprotected derivatives with the 1amino-3-azabicyclo[3.1.0]hexane and 1-amino-3-azabicyclo[4.1.0]heptane skeleton 10 have been synthesized by intramolecular reductive cyclopropanation of α-(N-allylamino)substituted N,N-dialkylcarboxamides 6, 8, and 9. Starting from derivatives of the naturally occurring amino acid serine (4a, 4b), the enantiomerically pure compounds 10a and 10b were obtained with endo/exo ratios of 2.5:1 (a) and 2:1 (b), in 26 and 30% overall yields, respectively. The unprotected bicyclic amines 11aa, 11ab, 11ba, and 11ad have been prepared by palladium-catalyzed hydrogenative deprotection of 10aa, 10ab, 10ba and 10ad, respectively, under acidic condi- [a]