Asymmetric carbon-carbon bond formation gamma to a carbonyl group: phosphine-catalyzed addition of nitromethane to allenes.
A chiral phosphine catalyzes the addition of a carbon nucleophile to the gamma position of an electron-poor allene (amide-, ester-, or phosphonate-substituted), in preference to isomerization to a 1,3-diene, in good ee and yield. This strategy provides an attractive method for the catalytic asymmetric gamma functionalization of carbonyl (and related) compounds.
Smith
Sean W
SW
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Fu
Gregory C
GC
D000447:Aldehydes / Q000138:chemical synthesis / Q000737:chemistry*; D000466:Alkadienes / Q000737:chemistry*; D000480:Alkynes / Q000737:chemistry; D002384:Catalysis; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D009595:Nitroparaffins / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry
D000447:Aldehydes; D000466:Alkadienes; D000480:Alkynes; D007659:Ketones; D009595:Nitroparaffins; D010720:Phosphines; C025947:propadiene; C044646:phosphine; D008697:Methane; C008640:nitromethane