title: Highly Efficient, Convergent, and Enantioselective Synthesis of Phthioceranic Acid.
abstract: A new strategy for highly concise, convergent, and enantioselective access to polydeoxypropionates has been developed. ZACA-Pd-catalyzed vinylation was used to prepare smaller deoxypropionate fragments, and then two key sequential Cu-catalyzed stereocontrolled sp(3)-sp(3) cross-coupling reactions allowed convergent assembly of smaller building blocks to build-up long polydeoxypropionate chains with excellent stereoselectivity. We employed this strategy for the synthesis of phthioceranic acid, a key constituent of the cell-wall lipid of Mycobacterium tuberculosis, in just 8 longest linear steps with full stereocontrol.
authors.affiliation: Herbert C. Brown Laboratories of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47907-2084 (USA).
authors.forename: Shiqing
authors.initials: S
authors.lastname: Xu
authors.affiliation: Herbert C. Brown Laboratories of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47907-2084 (USA).
authors.forename: Akimichi
authors.initials: A
authors.lastname: Oda
authors.affiliation: Herbert C. Brown Laboratories of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47907-2084 (USA).
authors.forename: Thomas
authors.initials: T
authors.lastname: Bobinski
authors.affiliation: Herbert C. Brown Laboratories of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47907-2084 (USA).
authors.forename: Haijun
authors.initials: H
authors.lastname: Li
authors.affiliation: Herbert C. Brown Laboratories of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47907-2084 (USA).
authors.forename: Yohei
authors.initials: Y
authors.lastname: Matsueda
authors.affiliation: Herbert C. Brown Laboratories of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47907-2084 (USA). negishi@purdue.edu.
authors.forename: Ei-ichi
authors.initials: E
authors.lastname: Negishi
mesh_terms: D000475:Alkenes / Q000737:chemistry; D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D002473:Cell Wall / Q000737:chemistry / Q000378:metabolism; D003300:Copper / Q000737:chemistry; D005227:Fatty Acids / Q000138:chemical synthesis / Q000737:chemistry*; D009169:Mycobacterium tuberculosis / Q000737:chemistry / Q000378:metabolism; D010165:Palladium / Q000737:chemistry; D011789:Quantum Theory; D013237:Stereoisomerism; D015040:Zirconium / Q000737:chemistry
chemical_list: D000475:Alkenes; D001688:Biological Products; D005227:Fatty Acids; C522296:phthioceranic acid; D010165:Palladium; D003300:Copper; D015040:Zirconium
keywords: ZACA reaction; asymmetric synthesis; cross-coupling; natural product synthesis; polydeoxypropionates