title: The synthesis of azadirachtin: a potent insect antifeedant.
abstract: We describe in full the first synthesis of the potent insect antifeedant azadirachtin through a highly convergent approach. An O-alkylation reaction is used to unite decalin ketone and propargylic mesylate fragments, after which a Claisen rearrangement constructs the central C8-C14 bond in a stereoselective fashion. The allene which results from this sequence then enables a second critical carbon-carbon bond forming event whereby the [3.2.1] bicyclic system, present in the natural product, is generated via a 5-exo-radical cyclisation process. Finally, using knowledge gained through our early studies into the reactivity of the natural product, a series of carefully designed steps completes the synthesis of this challenging molecule.
authors.affiliation: Department of Chemistry, University of Cambridge, UK. svl1000@cam.ac.uk
authors.forename: Steven V
authors.initials: SV
authors.lastname: Ley
authors.forename: Antonio
authors.initials: A
authors.lastname: Abad-Somovilla
authors.forename: James C
authors.initials: JC
authors.lastname: Anderson
authors.forename: Carles
authors.initials: C
authors.lastname: Ayats
authors.forename: Rolf
authors.initials: R
authors.lastname: Bänteli
authors.forename: Edith
authors.initials: E
authors.lastname: Beckmann
authors.forename: Alistair
authors.initials: A
authors.lastname: Boyer
authors.forename: Maria G
authors.initials: MG
authors.lastname: Brasca
authors.forename: Abigail
authors.initials: A
authors.lastname: Brice
authors.forename: Howard B
authors.initials: HB
authors.lastname: Broughton
authors.forename: Brenda J
authors.initials: BJ
authors.lastname: Burke
authors.forename: Ed
authors.initials: E
authors.lastname: Cleator
authors.forename: Donald
authors.initials: D
authors.lastname: Craig
authors.forename: Alastair A
authors.initials: AA
authors.lastname: Denholm
authors.forename: Ross M
authors.initials: RM
authors.lastname: Denton
authors.forename: Thomas
authors.initials: T
authors.lastname: Durand-Reville
authors.forename: Luca B
authors.initials: LB
authors.lastname: Gobbi
authors.forename: Michael
authors.initials: M
authors.lastname: Göbel
authors.forename: Brian Lawrence
authors.initials: BL
authors.lastname: Gray
authors.forename: Robert B
authors.initials: RB
authors.lastname: Grossmann
authors.forename: Claire E
authors.initials: CE
authors.lastname: Gutteridge
authors.forename: Norbert
authors.initials: N
authors.lastname: Hahn
authors.forename: Sarah L
authors.initials: SL
authors.lastname: Harding
authors.forename: David C
authors.initials: DC
authors.lastname: Jennens
authors.forename: Lynn
authors.initials: L
authors.lastname: Jennens
authors.forename: Peter J
authors.initials: PJ
authors.lastname: Lovell
authors.forename: Helen J
authors.initials: HJ
authors.lastname: Lovell
authors.forename: Mary L
authors.initials: ML
authors.lastname: de la Puente
authors.forename: Hartmuth C
authors.initials: HC
authors.lastname: Kolb
authors.forename: Win-Jan
authors.initials: WJ
authors.lastname: Koot
authors.forename: Sarah L
authors.initials: SL
authors.lastname: Maslen
authors.forename: Catherine F
authors.initials: CF
authors.lastname: McCusker
authors.forename: Amos
authors.initials: A
authors.lastname: Mattes
authors.forename: Andrew R
authors.initials: AR
authors.lastname: Pape
authors.forename: Andrea
authors.initials: A
authors.lastname: Pinto
authors.forename: Dinos
authors.initials: D
authors.lastname: Santafianos
authors.forename: James S
authors.initials: JS
authors.lastname: Scott
authors.forename: Stephen C
authors.initials: SC
authors.lastname: Smith
authors.forename: Andrew Q
authors.initials: AQ
authors.lastname: Somers
authors.forename: Christopher D
authors.initials: CD
authors.lastname: Spilling
authors.forename: Frank
authors.initials: F
authors.lastname: Stelzer
authors.forename: Peter L
authors.initials: PL
authors.lastname: Toogood
authors.forename: Richard M
authors.initials: RM
authors.lastname: Turner
authors.forename: Gemma E
authors.initials: GE
authors.lastname: Veitch
authors.forename: Anthony
authors.initials: A
authors.lastname: Wood
authors.forename: Cornelia
authors.initials: C
authors.lastname: Zumbrunn
mesh_terms: D007306:Insecticides / Q000138:chemical synthesis* / Q000737:chemistry; D036701:Limonins / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation; D013237:Stereoisomerism
chemical_list: D007306:Insecticides; D036701:Limonins; C010329:azadirachtin