Access to Nitriles from Aldehydes Mediated by an Oxoammonium Salt1. Issue 14 (9th February 2015)

• Record Type: Journal Article
• Authors: Kelly, Christopher B.; Lambert, Kyle M.; Mercadante, Michael A.; Ovian, John M.; Bailey, William F.; Leadbeater, Nicholas E.
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 14(2015)
• Page Start: 4241
• Page End: 4245
• Publication Date: 2015-02-09
• Subjects: aldehydes -- cyanides -- oxidation -- reaction mechanisms -- synthetic methods; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201412256
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A scalable, high yielding, rapid route to access an array of nitriles from aldehydes mediated by an oxoammonium salt (4‐acetylamino‐2, 2, 6, 6‐tetramethylpiperidine‐1‐oxoammonium tetrafluoroborate) and hexamethyldisilazane (HMDS) as an ammonia surrogate has been developed. The reaction likely involves two distinct chemical transformations: reversible silyl‐imine formation between HMDS and an aldehyde, followed by oxidation mediated by the oxoammonium salt and desilylation to furnish a nitrile. The spent oxidant can be easily recovered and used to regenerate the oxoammonium salt oxidant. Abstract : A serendipitous find : The scalable and high yielding title reaction is mediated by 4‐acetylamino‐2, 2, 6, 6‐tetramethylpiperidine‐1‐oxoammonium tetrafluoroborate and hexamethyldisilazane (HMDS). The reaction likely involves reversible silyl‐imine formation between HMDS and an aldehyde, and subsequent oxidation and desilylation. The spent oxidant can be easily recycled.