Asymmetric 1,4-reductions of hindered beta-substituted cycloalkenones using catalytic SEGPHOS-ligated CuH.
The reagent combination of catalytic amounts of copper hydride ligated by a nonracemic SEGPHOS ligand leads in situ to an extremely reactive species capable of effecting asymmetric hydrosilylations of conjugated cyclic enones in very high ees. An unprecedented substrate-to-ligand ratio as high as 275 000:1 for this transformation has been documented. [reaction: see text]
Lipshutz
Bruce H
BH
Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA 93106, USA. lipshutz@chem.ucsb.edu
Servesko
Jeff M
JM
Petersen
Tue B
TB
Papa
Patrick P
PP
Lover
Andrew A
AA
D000970:Antineoplastic Agents / Q000138:chemical synthesis* / Q000494:pharmacology; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D003512:Cyclohexanones / Q000138:chemical synthesis* / Q000494:pharmacology; D007659:Ketones / Q000737:chemistry*; D008024:Ligands; D015394:Molecular Structure; D017646:Organosilicon Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D013237:Stereoisomerism
D000970:Antineoplastic Agents; D003512:Cyclohexanones; D007659:Ketones; D008024:Ligands; D017646:Organosilicon Compounds; D003300:Copper