1,2-Radical Shifts in Photoinduced Synthetic Organic Transformations: A Guide to the Reactivity of Useful Radical Synthons DOI Creative Commons
Bianca T. Matsuo, Albert Granados, Jadab Majhi

et al.

ACS Organic & Inorganic Au, Journal Year: 2022, Volume and Issue: 2(6), P. 435 - 454

Published: Aug. 15, 2022

The exploration of 1,2-radical shift (RS) mechanisms in photoinduced organic reactions has provided efficient routes for the generation important radical synthons many chemical transformations. In this Review, basic concepts involved traditional 1,2-spin-center (SCS) recently reported studies are discussed. addition, other useful 1,2-RSs addressed, such as those proceeding through 1,2-group migrations carbohydrate chemistry, via 1,2-boron shifts, and by α-amino radicals. discussion begins with a general overview aspects 1,2-RS mechanisms, followed demonstration their applicability sections that follow organized according to operating combination migration event. This contribution is not comprehensive review but rather aims provide an understanding topic, focused on more recent advances field, establishes definition nomenclature been used describe mechanisms.

Language: Английский

The interplay of polar effects in controlling the selectivity of radical reactions DOI
Alessandro Ruffoni, Rory C. Mykura, Massimo Bietti

et al.

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(9), P. 682 - 695

Published: Aug. 1, 2022

Language: Английский

Citations

98
Excited-State Palladium-Catalyzed Radical Migratory Mizoroki–Heck Reaction Enables C2-Alkenylation of Carbohydrates DOI
Wang Yao, Gaoyuan Zhao, Yue Wu

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(8), P. 3353 - 3359

Published: Feb. 21, 2022

Excited-state palladium catalysis has emerged as a promising strategy for developing novel and valuable reactions. Herein, we report the first excited-state Pd-catalyzed 1,2-radical migratory Mizoroki–Heck reaction that enables C2-alkenylation of carbohydrates using readily available 1-bromosugars alkenes. The tolerates wide variety functional groups complex molecular architectures, including derivatives natural products marketed drugs. Preliminary mechanistic studies DFT calculations suggest involvement visible-light-induced photoexcitation Pd species, 1,2-spin-centered-shift (SCS) process, Heck-type cross-coupling reaction. expands reactivity profile provides streamlined protocol preparation C2-alkenylated carbohydrate mimetics to aid discovery development new therapeutics, agrochemicals, materials.

Language: Английский

Citations

75
Catalytic Approaches to Chemo- and Site-Selective Transformation of Carbohydrates DOI
Kenzo Yamatsugu, Motomu Kanai

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(10), P. 6793 - 6838

Published: April 26, 2023

Carbohydrates are a fundamental unit playing pivotal roles in all the biological processes. It is thus essential to develop methods for synthesizing, functionalizing, and manipulating carbohydrates further understanding of their functions creation sugar-based functional materials. is, however, not trivial such methods, since densely decorated with polar similarly reactive hydroxy groups stereodefined manner. New approaches chemo- site-selective transformations are, therefore, great significance revolutionizing sugar chemistry enable easier access sugars interest. This review begins brief overview innate reactivity carbohydrates. followed by discussions about catalytic enhance, override, or be orthogonal transformation avoids making list reactions, but rather focuses on summarizing concept behind each reported transformation. The literature references were sorted into sections based underlying ideas approaches, which we hope will help readers have better sense current state innovative field.

Language: Английский

Citations

49
Transformations of carbohydrate derivatives enabled by photocatalysis and visible light photochemistry DOI Creative Commons

Daniel J. Gorelik,

Shrey P. Desai,

Sofia Jdanova

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(4), P. 1204 - 1236

Published: Jan. 1, 2024

This review article highlights the diverse ways in which recent developments areas of photocatalysis and visible light photochemistry are impacting synthetic carbohydrate chemistry.

Language: Английский

Citations

30
Excited-State Palladium-Catalyzed 1,2-Spin-Center Shift Enables Selective C-2 Reduction, Deuteration, and Iodination of Carbohydrates DOI
Gaoyuan Zhao, Wang Yao, Jaclyn N. Mauro

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(4), P. 1728 - 1734

Published: Jan. 19, 2021

Excited-state catalysis, a process that involves one or more excited catalytic species, has emerged as powerful tool in organic synthesis because it allows access to the excited-state reaction landscape for discovery of novel chemical reactivity. Herein, we report first palladium-catalyzed 1,2-spin-center shift enables site-selective functionalization carbohydrates. The strategy features mild conditions with high levels regio- and stereoselectivity tolerate wide range functional groups complex molecular architectures. Mechanistic studies suggest radical mechanism involving formation hybrid palladium species undergoes followed by reduction, deuteration, iodination afford functionalized 2-deoxy sugars. new reactivity will provide general approach rapid generation natural unnatural

Language: Английский

Citations

90
Selective Isomerization via Transient Thermodynamic Control: Dynamic Epimerization of trans to cis Diols DOI
Christian J. Oswood, David W. C. MacMillan

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 144(1), P. 93 - 98

Published: Dec. 22, 2021

Traditional approaches to stereoselective synthesis require high levels of enantio- and diastereocontrol in every step that forms a new stereocenter. Here, we report an alternative approach, which the stereochemistry organic substrates is selectively edited without further structural modification, strategy with potential allow classes late-stage stereochemical manipulation provide access rare or valuable configurations. In this work, describe selective epimerization cyclic diols enabled by hydrogen atom transfer photocatalysis boronic acid mediated transient thermodynamic control, generating less stable cis products from otherwise favored trans isomers. A range substitution patterns ring sizes are amenable isomerization, including stereochemically complex polyols such as estriol, well syn anti acyclic vicinal diols. Moreover, has divergent saccharide anomers, providing distinct sugar isomers α- β-configured glycosides.

Language: Английский

Citations

74
Quinuclidine and its derivatives as hydrogen-atom-transfer catalysts in photoinduced reactions DOI
Wei Xiao, Xinhua Wang,

Ruixiu Liu

et al.

Chinese Chemical Letters, Journal Year: 2021, Volume and Issue: 32(6), P. 1847 - 1856

Published: Feb. 10, 2021

Language: Английский

Citations

59
Selective Axial-to-Equatorial Epimerization of Carbohydrates DOI
Hayden M. Carder, Yong Wang, Alison E. Wendlandt

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(26), P. 11870 - 11877

Published: June 22, 2022

Radical-mediated transformations have emerged as powerful methods for the synthesis of rare and unnatural branched, deoxygenated, isomeric sugars. Here, we describe a radical-mediated axial-to-equatorial alcohol epimerization method to transform abundant glycans into isomers. The delivers highly predictable selective reaction outcomes that are complementary other sugar isomerization methods. synthetic utility isomer interconversion is showcased through expedient glycan synthesis, including one-step glycodiversification. Mechanistic studies reveal both site- diastereoselectivities achieved by H atom abstraction equatorially disposed α-hydroxy C–H bonds.

Language: Английский

Citations

55
Exploiting photoredox catalysis for carbohydrate modification through C–H and C–C bond activation DOI
Andrey Shatskiy, Elena V. Stepanova, Markus D. Kärkäs

et al.

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(11), P. 782 - 805

Published: Sept. 21, 2022

Language: Английский

Citations

49
Application of the Spin-Center Shift in Organic Synthesis DOI Creative Commons
Feng‐Lian Zhang, Bin Li, K. N. Houk

et al.

JACS Au, Journal Year: 2022, Volume and Issue: 2(5), P. 1032 - 1042

Published: April 11, 2022

Spin-center shift (SCS) is a radical process involving 1,2-radical translocation along with two-electron ionic movement, such as elimination of an adjacent leaving group. Such was initially observed in some important biochemical transformations, and the unique property has also attracted considerable interest synthetic chemistry. Experimental, kinetic, well computational studies have been performed, series useful transformations developed applied organic synthesis based on SCS processes last 20 years. This Perspective overview mechanism.

Language: Английский

Citations

48