Photochemical alkynylation of hydrosilanes by iron catalysis

Abstract

Alkynylsilanes is one kind of essential synthetic block in organic chemistry. The established synthetic routes remain some drawbacks regarding to harsh reaction conditions or expensive/rare metal catalyst. Herein, we report...

Ni-catalyzed cross-coupling of heteroaryl sulfones and diselenides via deheteroaromatization and heteroaromatization: synthesis of heteroaryl selenides

“…Based on the above facts and relevant literature reports, 14 we propose a plausible reaction mechanism (Fig. 4).…”

Merging Photoinduced Iron-Catalyzed Decarboxylation with Copper Catalysis for C–N and C–C Couplings

“…The photochemistry plays indispensable roles in organic synthesis since it could facilitate the formation of the reactive single-electron species and enable inert bond cleavages under mild conditions . Among them, the photoinduced iron catalysis has significantly drawn chemists’ attention since iron is the most abundant and low-cost transition metal. , The early works have disclosed that, in the presence of visible light, the excited iron catalyst might typically undergo the ligand-to-iron charge transfer (Fe­(III)–X to Fe­(II) and X·) and then facilitate the formation of the reactive carbon radicals, particularly the unstabilized alkyl radicals, by cleaving the C–H or O–H bonds (Scheme -i), providing efficient tools to construct C–C, C–N, C–O, and C–X bonds . Studies have typically focused on (i) radical addition to the unsaturated units (Scheme -i, path a), such as electron-deficient alkenes, diazene diesters, (hetero)­aryl rings, RNO x , O 2 , etc., to form bonds by the radical delivery and (ii) the radical trapping with electrophilic halogen reagents, such as NIS, NBS, or Selectfluor, to build the C–X bonds (Scheme -i, path b) .…”

Synthesis of Alkynylsilanes: A Review of the State of the Art

“…In this process, they found that the optimal conditions involved a combination of light, 10 mol% of iron(III) chloride, and 0.5 equivalents of lithium chloride in acetonitrile at room temperature (Figure 30). [141] The procedure worked selectively in the presence of various ethynyl phenyl sulfones and hydrosilanes ( e. g ., Ph 2 SiH 2 , Et 3 SiH, PhMe 2 SiH, etc .). The formation of silyl radicals was validated through various experiments.…”