Toolbox for Distal C–H Bond Functionalizations in Organic Molecules

Chemical Reviews, Год журнала: 2021, Номер 122(6), С. 5682 - 5841

Опубликована: Окт. 18, 2021

Transition-metal-catalyzed C–H activation has developed a contemporary approach to the omnipresent area of retrosynthetic disconnection. Scientific researchers have been tempted take help this methodology plan their synthetic discourses. This paradigm shift helped in development industrial units as well, making synthesis natural products and pharmaceutical drugs step-economical. In vast zone bond activation, functionalization proximal bonds gained utmost popularity. Unlike bonds, distal is more strenuous requires distinctly specialized techniques. review, we compiled various methods adopted functionalize mechanistic insights within each these procedures, scope methodology. With give complete overview expeditious progress made field organic chemistry while also highlighting its pitfalls, thus leaving open for further modifications.

Язык: Английский

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Visible light photocatalysis in the late-stage functionalization of pharmaceutically relevant compounds

Chemical Society Reviews, Год журнала: 2020, Номер 50(2), С. 766 - 897

Опубликована: Дек. 22, 2020

Recent developments and future prospects of visible-light photocatalysis in the late-stage functionalization pharmaceuticals natural bioactive compounds.

Язык: Английский

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Visible light photoredox-catalysed remote C–H functionalisation enabled by 1,5-hydrogen atom transfer (1,5-HAT)

Chemical Society Reviews, Год журнала: 2021, Номер 50(13), С. 7359 - 7377

Опубликована: Янв. 1, 2021

The generation of heteroatom-centred radicals followed by intramolecular 1,5-HAT and functionalisation the translocated carbon-centred radical is an efficient way to functionalize chemo- regio-selectively remote unactivated C(sp³)–H bond.

Язык: Английский

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Copper-catalyzed radical relay in C(sp³)–H functionalization

Chemical Society Reviews, Год журнала: 2022, Номер 51(5), С. 1640 - 1658

Опубликована: Янв. 1, 2022

Radical-involved transition metal (TM) catalysis has greatly enabled new reactivities in recent decades. Copper-catalyzed radical relay offers enormous potential C(sp3)-H functionalization which combines the unique regioselectivity of hydrogen atom transfer (HAT) and versatility copper-catalyzed cross-coupling. More importantly, significant progress been achieved asymmetric C-H through judicious ligand design. This tutorial review will highlight advances this rapidly growing area, we hope survey inspire future strategic developments for selective functionalization.

Язык: Английский

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Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Chemical Reviews, Год журнала: 2024, Номер 124(17), С. 10192 - 10280

Опубликована: Авг. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Язык: Английский

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Deconstructive Functionalizations of Unstrained Carbon–Nitrogen Cleavage Enabled by Difluorocarbene

ACS Central Science, Год журнала: 2020, Номер 6(10), С. 1819 - 1826

Опубликована: Авг. 31, 2020

Transition-metal- or oxidant-promoted deconstructive functionalizations of noncyclic carbon–nitrogen bonds are well established, usually only leaving one moiety functionalized toward the final product. In contrast, concomitant C- and N-functionalizations via unstrained C(sp3)–N bond under metal- oxidant-free conditions very rare, which would favorably confer versatility product diversity. Disclosed herein is first difluorocarbene-induced embodying successive cleavage cyclic amines synchronous functionalization both constituent atoms be preserved in eventual molecular outputs transition-metal-free conditions. Correspondent access to deuterated formamides with ample isotopic incorporation was demonstrated by a switch heavy water conceivably useful pharmaceutical sciences. The current strategy remarkably administers convenient, operationally simple novel method diversity from readily available starting materials. Therefore, we project that these findings broad interest research endeavors encompassing fluorine chemistry, carbene C–N activation, as medicinal chemistry.

Язык: Английский

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Alkene versus alkyne reactivity in unactivated 1,6-enynes: regio- and chemoselective radical cyclization with chalcogens under metal- and oxidant-free conditions

Green Chemistry, Год журнала: 2020, Номер 22(7), С. 2288 - 2300

Опубликована: Янв. 1, 2020

Substituted pyrrolidine derivatives are obtained via regio- and chemoselective 5-exo-dig radical cyclization of unactivated 1,6-enynes with chalcogens under metal- oxidant-free conditions.

Язык: Английский

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Radical Functionalization of Remote C(sp ³ )–H Bonds Mediated by Unprotected Alcohols and Amides

CCS Chemistry, Год журнала: 2020, Номер 2(5), С. 813 - 828

Опубликована: Июнь 10, 2020

Aliphatic alcohols and amides are highly valued, ubiquitous chemicals in synthetic chemistry. Radical-promoted regioselective functionalization of unactivated C(sp3)–H bonds offers an atom step...

Язык: Английский

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Intermolecular 1,2-Difunctionalization of Alkenes Enabled by Fluoroamide-Directed Remote Benzyl C(sp³)–H Functionalization

Journal of the American Chemical Society, Год журнала: 2021, Номер 144(1), С. 339 - 348

Опубликована: Дек. 22, 2021

A copper-catalyzed remote benzylic C-H functionalization strategy enabling 1,2-difunctionalization of alkenes with 2-methylbenzeneamides and nucleophiles, including alcohols, indoles, pyrroles, the intrinsic amino groups, is reported, which characterized by its redox-neutral conditions, exquisite site-selectivity, broad substrate scope, wide utilizations late-stage modifying bioactive molecules. This reaction proceeds through nitrogen-centered radical generation, hydrogen atom transfer, addition across alkenes, single-electron oxidation, carbocation electrophilic course cascades. While using external nucleophiles manipulates three-component alkene alkylalkoxylation alkyl-heteroarylation to access dialkyl ethers, 3-alkylindoles, 3-alkylpyrroles, omitting results in two-component alkylamidation ([5+2] annulation) benzo-[f][1,2]thiazepine 1,1-dioxides.

Язык: Английский

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Metal-free photoinduced hydrogen atom transfer assisted C(sp³)–H thioarylation

Green Chemistry, Год журнала: 2023, Номер 25(9), С. 3431 - 3436

Опубликована: Янв. 1, 2023

A mild metal-free approach for C(sp 3 )–H thioarylation of organic building blocks.

Язык: Английский

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