Pd-catalyzed asymmetric allylic alkylation. A short route to the cyclopentyl core of viridenomycin.
A palladium-catalyzed asymmetric allylic alkylation effects a dynamic kinetic asymmetric transformation of racemic isoprene monoepoxide and a surrogate for Nazarov's reagent in which a quaternary center is created with exellent ee. The resultant adduct allows easy access to a substrate for ring-closing metathesis to form a cyclopentenone and sets the stage for an 11-step synthesis of the cyclopentyl core of the antibiotic antitumor agent viridenomycin. [reaction: see text]
Trost
Barry M
BM
Department of Chemistry, Stanford University, Stanford, CA 94305-5080, USA. bmtrost@stanford.edu
Jiang
Chunhui
C
D000478:Alkylation; D000498:Allyl Compounds / Q000737:chemistry*; D000903:Antibiotics, Antineoplastic / Q000138:chemical synthesis; D002070:Butadienes / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D003517:Cyclopentanes / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry; D045782:Hemiterpenes; D007769:Lactams / Q000138:chemical synthesis*; D009942:Organometallic Compounds / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*; D010420:Pentanes; D013237:Stereoisomerism
D000498:Allyl Compounds; D000903:Antibiotics, Antineoplastic; D002070:Butadienes; D003517:Cyclopentanes; D004852:Epoxy Compounds; D045782:Hemiterpenes; D007769:Lactams; D009942:Organometallic Compounds; D010420:Pentanes; C005059:isoprene; C010374:viridinomycin; D010165:Palladium