title: BF3-Mediated cis-Selective Cycloaddition of O-Silyloxime with Alkenes.
abstract: A C-amide-substituted O-silylated oxime, (E)-(tert-butyldimethylsiloxyimino)acetic acid N,N-dimethylamide (8b), on treatment with 2.2 equiv of BF3·OEt2, in situ generated boracyclic nitrone-type intermediate BF3·14, which underwent cycloaddition with alkenes to give 3,5-cis-isoxazolidines as the major products. The mechanism was strongly supported by isolation of the reaction intermediate 14 that was characterized by X-ray diffraction and its further reaction. This cycloaddition was successfully applied to the synthesis of syn-HPA-12 known as an inhibitor of CERT that mediates the transport of ceramide.
authors: †Showa Pharmaceutical University, Machida, Tokyo 194-8543, Japan.
authors: Nobuyoshi
authors: N
authors: Morita
authors: †Showa Pharmaceutical University, Machida, Tokyo 194-8543, Japan.
authors: Rina
authors: R
authors: Kono
authors: †Showa Pharmaceutical University, Machida, Tokyo 194-8543, Japan.
authors: Kenji
authors: K
authors: Fukui
authors: †Showa Pharmaceutical University, Machida, Tokyo 194-8543, Japan.
authors: Asuka
authors: A
authors: Miyazawa
authors: ‡Faculty of Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, Sanuki 769-2193, Japan.
authors: Hyuma
authors: H
authors: Masu
authors: ‡Faculty of Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, Sanuki 769-2193, Japan.
authors: Isao
authors: I
authors: Azumaya
authors: †Showa Pharmaceutical University, Machida, Tokyo 194-8543, Japan.
authors: Shintaro
authors: S
authors: Ban
authors: †Showa Pharmaceutical University, Machida, Tokyo 194-8543, Japan.
authors: Yoshimitsu
authors: Y
authors: Hashimoto
authors: †Showa Pharmaceutical University, Machida, Tokyo 194-8543, Japan.
authors: Iwao
authors: I
authors: Okamoto
authors: †Showa Pharmaceutical University, Machida, Tokyo 194-8543, Japan.
authors: Osamu
authors: O
authors: Tamura
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000577:Amides / Q000138:chemical synthesis* / Q000737:chemistry; D001880:Boranes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003500:Cyclization; D008958:Models, Molecular; D015394:Molecular Structure; D010091:Oximes / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D000577:Amides; D001880:Boranes; C441643:N-(3-hydroxy-1-hydroxymethyl-3-phenylpropyl)dodecanamide; D010091:Oximes; D012821:Silanes; C021274:boron trifluoride