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Visible-Light Induced Singlet Nucleophilic Carbenes: Rapid and Mild Access to Fluorinated Tertiary Alcohol Derivatives
preprintsubmitted on 19.12.2020, 08:55 and posted on 21.12.2020, 13:23 by Daniel Priebbenow, Rowan Pilkington, Anastasios Polyzos
Singlet nucleophilic carbenes (SNCs) that contain only one heteroatom donor remain underexplored and underutilized in chemical synthesis. To discover new synthetic strategies that harness these SNCs as reactive intermediates, aromatic or aliphatic siloxy carbenes represent excellent model substrates as they can be readily generated photochemically from stable acyl silane precursors. We herein report the discovery that photochemically generated siloxy carbenes undergo 1,2-carbonyl addition to trifluoromethyl ketones, followed by a silyl transfer process to afford benzoin-type products. This new transformation is a rare example of the use of ketones as trapping reagents for SNC intermediates and delivers an efficient, user-friendly and scalable process to access fluorinated tertiary alcohol derivatives driven by only light, circumventing the use of catalysts or additives.