Enantioselective Organocatalytic Conjugate Addition of Aldehydes to Vinyl Sulfones and Vinyl Phosphonates as Challenging Michael Acceptors

• Published in: Chemistry : a European journal 2009-03, Vol.15 (13), p.3204-3220
• Main Authors: Sulzer‐Mossé, Sarah, Alexakis, Alexandre, Mareda, Jiri, Bollot, Guillaume, Bernardinelli, Gerald, Filinchuk, Yaroslav
• Format: Article
• Language: English
• Subjects: aldehydes; Aldehydes - chemical synthesis; Aldehydes - chemistry; amines; Amines - chemistry; asymmetric synthesis; Catalysis; Combinatorial Chemistry Techniques; Michael addition; Models, Chemical; Molecular Structure; organocatalysis; Organophosphonates - chemical synthesis; Organophosphonates - chemistry; Pyrrolidines - chemistry; Stereoisomerism; Sulfones - chemical synthesis; Sulfones - chemistry; Vinyl Compounds - chemical synthesis; Vinyl Compounds - chemistry
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200801892

Chiral framework: Chiral amines with pyrrolidine frameworks catalyze the enantioselective conjugate addition of a wide range of aldehydes to various vinyl sulfones and vinyl phosphonates in high yields and with enantioselectivities up to >99 % ee (see scheme). The high versatility of the Michael adducts is exemplified by various functionalizations with conservation of the optical purity. Chiral amines with a pyrrolidine framework catalyze the enantioselective conjugate addition of a broad range of aldehydes to various vinyl sulfones and vinyl phosphonates in high yields and with enantioselectivities up to >99 % ee. This novel process provides synthetically useful chiral γ‐gem‐sulfonyl or phosphonyl aldehydes which can be widely functionalized with retention of the enantiomeric excess. Mechanistic insights including DFT calculations are explored in detail. Chiral framework: Chiral amines with pyrrolidine frameworks catalyze the enantioselective conjugate addition of a wide range of aldehydes to various vinyl sulfones and vinyl phosphonates in high yields and with enantioselectivities up to >99 % ee (see scheme). The high versatility of the Michael adducts is exemplified by various functionalizations with conservation of the optical purity.