Photocatalyzed dehalogenative deuteration with silacarboxylic acids as halogen-atom transfer agents

Abstract

Deuterated chemicals are widely utilized in a broad range of disciplines and dehalogenative deuteration of organohalides represents a promising approach to obtaining deuterated chemicals. Herein, we disclose a visible light-induced organophotocatalytic strategy for dehalogenative deuteration of a wide variety of primary, secondary, and tertiary alkyl bromides. Key to this protocol is silyl radical-promoted halogen-atom transfer and thiol-mediated deuterium-atom transfer. Readily available silacarboxylic acids, which generate silyl radicals through efficient visible-light-induced decarboxylation, are applied as halogen-atom transfer agents. The protocol employs economical deuterium oxide as the source of deuterium. Late stage deuteration of complex natural products and drug derivatives demonstrated the potential of this environmentally benign method for practical applications.