Development of Regio- and Face-selective [2+3] Cycloaddition Reactions of Readily Preparable Oxime-substituted Nitrile Oxides with Silicon-linked Allylic-alcohol Moieties for Intramolecular Reactions

Nitrile oxides are typically prepared in situ from nitroalkanes and converted to 2-isoxazoline heterocycles upon [2 + 3] cycloaddition with alkenes, providing synthetically useful intermediates such as beta-hydroxy ketones and gamma-amino alcohols. Herein, we prepared oxime-substituted nitrile oxides bound to allylic-alcohol derivatives through a silicon atom and demonstrated their intramolecular cycloaddition reactions. The desired cycloadducts were obtained as single regioisomers in good yields. Furthermore, face-selective cycloaddition reactions were achieved using alpha-substituted allylic-alcohol derivatives, affording the desired cycloadducts with high diastereoselectivity.