Single‐Atom Catalysis in Organic Synthesis

Abstract

Single‐atom catalysts hold the potential to significantly impact the chemical sector, pushing the boundaries of catalysis in new, uncharted directions. These materials, featuring isolated metal species ligated on solid supports, can exist in many coordination environments, all of which have shown important functions in specific transformations. Their emergence has also provided exciting opportunities for mimicking metalloenzymes and bridging the gap between homogeneous and heterogeneous catalysis. This Review outlines the impressive progress made in recent years regarding the use of single‐atom catalysts in organic synthesis. We also illustrate potential knowledge gaps in the search for more sustainable, earth‐abundant single‐atom catalysts for synthetic applications.

Photo-Induced Electrophilic Aromatic Substitution of Ferric Acyl Nitrene

“…: 200−202℃. 1 H NMR (400 MHz, CDCl3) δ 9.76 (s, 1H), 7.14-7.12 (m, 2H), 6.86-6.84 (m, 2H), 4.61 (s, 2H), 2.59 (q, J= 24Hz, 2H), 1.33 (s, 9H), 1.20 (t, J= 16Hz, 3H). ; 13 C{ 1 H} NMR (101 MHz, CDCl3) δ 176.0, 165.6, 155.1, 138.2, 129.0, 114.6, 67.4, 38.4, 28.0, 27.0, 15.7.…”

“…; 13 C{ 1 H} NMR (101 MHz, CDCl3) δ 176. 1,165.3,159.2,155.1 (d,J= 370Hz),116.2 (d,J= 20Hz),116.0 (d,J= 10Hz),67.7,38.4,26.9.…”

“…33 mg (71% yield); mp.:190-191℃. 1 H NMR (400 MHz, CDCl3) δ 9.59 (s, 1H), 6.79-6.76 (m, 3H), 4.60 (s, 2H), 2.28 (s, 3H). ; 13 C{ 1 H} NMR (101 MHz, CDCl3) δ 166.…”

“…Apart from reaction efficiency, transformation selectivity control is one of the most important issues in field of organic synthesis. 1 As such, "precise chemistry" has been invented, and a series of synthons served as powerful substrates towards selective preparation of various scaffolds with high structural diversity and functional-group complexity. 2 Nitrene species, well-recognized as a history-long reactive intermediate, attracted continuous interests of synthetic chemists, and various nitrene-involved transformations have been developed.…”

Selective hydrogenation of lignocellulosic biomass over single-atom catalysts

“…For example, SACs have displayed unique advantages for the hydrogenation of biobased chemicals. 19,28 SACs can selectively activate the polar functional groups such as CO by dissociating H 2 through heterolysis to form M–H δ − species while suppress the hydrogenation of CC bonds that are conventionally induced by the homolysis of H 2 . 29,30 Besides, the unique vertical C–O bond adsorption configuration of SACs can substantially inhibit ring hydrogenation and enhance product selectivity in the hydrodeoxygenation (HDO) reactions.…”