title: Catalytic asymmetric crotylation of aldehydes: application in total synthesis of (-)-elisabethadione.
abstract: A new, highly efficient Lewis base catalyst for a practical enantio- and diastereoselective crotylation of unsaturated aldehydes with E- and Z-crotyltrichlorosilanes has been developed. The method was employed as a key step in a novel asymmetric synthesis of bioactive serrulatane diterpene (-)-elisabethadione. Other strategic reactions for setting up the stereogenic centers included anionic oxy-Cope rearrangement and cationic cyclization. The synthetic route relies on simple, high yielding reactions and avoids use of protecting groups or chiral auxiliaries.
authors: Department of Chemistry, Loughborough University, Loughborough, LE11 3TU (UK), Fax: (+44) 1509 22 3925.
authors: Paul S
authors: PS
authors: O'Hora
authors: Celia A
authors: CA
authors: Incerti-Pradillos
authors: Mikhail A
authors: MA
authors: Kabeshov
authors: Sergei A
authors: SA
authors: Shipilovskikh
authors: Aleksandr E
authors: AE
authors: Rubtsov
authors: Mark R J
authors: MR
authors: Elsegood
authors: Andrei V
authors: AV
authors: Malkov
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D003500:Cyclization; D008968:Molecular Conformation; D009285:Naphthoquinones / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D009285:Naphthoquinones; C519818:elisabethadione
keywords: allylation; asymmetric catalysis; rearrangement; stereoselectivity; total synthesis