Z-Selective Alkyne Semireduction by an Organic Photoreductant.

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Tác giả: Benjamin R G Bissinger, Henric F Janning, Dang H Vu, Mario P Wiesenfeldt

Ngôn ngữ: eng

Ký hiệu phân loại: 809.008 History and description with respect to kinds of persons

Thông tin xuất bản: Germany : Angewandte Chemie (International ed. in English) , 2025

Mô tả vật lý:

Bộ sưu tập: NCBI

ID: 719229

The semireduction of alkynes is an indispensable transformation for the synthesis of Z-alkenes. Although extensive studies with mostly transition metal-based catalysts have enabled it to produce a broad scope of alkenes, a Scifinder search and a robustness screen of Lindlar's catalyst indicate that highly Lewis-basic nitrogen and sulfur-containing motifs, which are prevalent in drugs, remain problematic. Herein, we report an alkyne semi-reduction using an organic photoreductant that tolerates all 10 of the most common Lewis-basic motifs in drugs. The reaction reduces terminal alkyl and aryl, dialkyl, alkyl aryl, and diaryl alkynes in high yields and Z-selectivities, while tolerating other reducible motifs like sulfones, nitriles, ketones, and electron-poor arenes. UV/Vis and NMR titration studies indicate that the reaction occurs by formation of a photoexcitable electron donor-acceptor (EDA) complex. Furthermore, a time study indicated that the reductant enforces a Z-selective reaction, which is unusual for alkyne reductions via electron transfer.
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