title: Palladium-catalyzed chemoselective allylic substitution, Suzuki-Miyaura cross-coupling, and allene formation of bifunctional 2-B(pin)-substituted allylic acetate derivatives.
abstract: A formidable challenge at the forefront of organic synthesis is the control of chemoselectivity to enable the selective formation of diverse structural motifs from a readily available substrate class. Presented herein is a detailed study of chemoselectivity with palladium-based phosphane catalysts and readily available 2-B(pin)-substituted allylic acetates, benzoates, and carbonates. Depending on the choice of reagents, catalysts, and reaction conditions, 2-B(pin)-substituted allylic acetates and derivatives can be steered into one of three reaction manifolds: allylic substitution, Suzuki-Miyaura cross-coupling, or elimination to form allenes, all with excellent chemoselectivity. Studies on the chemoselectivity of Pd catalysts in their reactivity with boron-bearing allylic acetate derivatives led to the development of diverse and practical reactions with potential utility in synthetic organic chemistry.
authors: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, PA 19104-6323 (USA), Fax: (+1) 12155736743.
authors: Byeong-Seon
authors: BS
authors: Kim
authors: Mahmud M
authors: MM
authors: Hussain
authors: Nusrah
authors: N
authors: Hussain
authors: Patrick J
authors: PJ
authors: Walsh
mesh_terms: D000085:Acetates / Q000138:chemical synthesis* / Q000737:chemistry*; D000466:Alkadienes / Q000138:chemical synthesis* / Q000737:chemistry*; D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D008958:Models, Molecular; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000085:Acetates; D000466:Alkadienes; D000498:Allyl Compounds; C025947:propadiene; D010165:Palladium; C498551:allyl acetate
keywords: allenes; allylic substitution; chemoselectivity; cross-coupling; palladium