Desulfonylation via Radical Process: Recent Developments in Organic Synthesis

Chemical Reviews, Год журнала: 2021, Номер 121(20), С. 12548 - 12680

Опубликована: Авг. 13, 2021

As the "chemical chameleon", sulfonyl-containing compounds and their variants have been merged with various types of reactions for efficient construction diverse molecular architectures by taking advantage incredible reactive flexibility. Currently, involvement in radical transformations, which sulfonyl group typically acts as a leaving via selective C–S, N–S, O–S, S–S, Se–S bond cleavage/functionalization, has facilitated new formation strategies are complementary to classical two-electron cross-couplings organometallic or ionic intermediates. Considering great influence synthetic potential these novel avenues, we summarize recent advances this rapidly expanding area discussing reaction designs, substrate scopes, mechanistic studies, limitations, outlining state-of-the-art processes involved radical-mediated desulfonylation related transformations. With specific emphasis on applications, believe review will be useful medicinal organic chemists who interested chemistry particular.

Язык: Английский

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Beyond classical sulfone chemistry: metal- and photocatalytic approaches for C–S bond functionalization of sulfones

Chemical Society Reviews, Год журнала: 2022, Номер 51(15), С. 6774 - 6823

Опубликована: Янв. 1, 2022

Sulfones are excellent candidates for the design of new C–C and C–X bond-forming reactions owing to easy activation C–S bonds. This review focuses on challenges recent opportunities catalytic functionalization sulfones.

Язык: Английский

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Rhodium Catalyzed Regioselective C−H Allylation of Simple Arenes via C−C Bond Activation of Gem‐difluorinated Cyclopropanes

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(19), С. 10626 - 10631

Опубликована: Фев. 18, 2021

Herein, we report a rhodium catalyzed directing-group free regioselective C-H allylation of simple arenes. Readily available gem-difluorinated cyclopropanes can be employed as highly reactive allyl surrogates via sequence C-C and C-F bond activation, providing arene derivatives in good yields with high regioselectivity under mild conditions. The robust methodology enables facile late-stage functionalization complex bioactive molecules. efficiency this reaction is also demonstrated by the turnover number (TON, up to 1700) catalyst on gram-scale experiments. Preliminary success kinetic resolution transformation achieved, promising access enantio-enriched cyclopropanes.

Язык: Английский

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Pd/NHC-Controlled Regiodivergent Defluorinative Allylation of gem-Difluorocyclopropanes with Allylboronates

ACS Catalysis, Год журнала: 2022, Номер 12(11), С. 6495 - 6505

Опубликована: Май 17, 2022

Controlling the selectivity of synthetically useful reactions has been a longstanding objective organic chemistry. We report regiodivergent synthetic protocol allowing access to diverse fluorinated 1,5-dienes through Pd/NHC-catalyzed ring-opening allylation gem-difluorocyclopropanes. Density functional theory (DFT) calculations on regioselectivity-determining transition states provided critical insight into design NHC ligand for switching regioselectivity. Consistent with DFT predictions, N-heterocyclic carbene (NHC) ligands bulky ortho substituents favored branched allylation, IHept providing > 20:1 branched/linear less hindered such as IMes thermodynamically more stable linear products. were able carry out late-stage modification various complex molecules using this protocol. Our ligand-controlled approach provides efficient regioisomeric from same starting materials and constitutes valuable addition toolbox diversity-oriented synthesis.

Язык: Английский

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Catalytic Diversification of gem‐Difluorocyclopropanes: Recent Advances and Challenges

ChemCatChem, Год журнала: 2022, Номер 14(24)

Опубликована: Авг. 11, 2022

Abstract gem ‐Difluorocyclopropanes (F 2 CPs) have aroused considerable attention not only from the structural perspective but also due to their ability participate in various valuable transformations. This Review summarizes advances catalytic ring‐opening reactions of ‐F CPs, especially emphasizing reactivities and applications those non‐activated ones under transition‐metal catalysis. Their achievements, synthetic limitations are discussed with aim stimulate enthusiasm for further development.

Язык: Английский

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Photoredox-catalyzed C–C bond cleavage of cyclopropanes for the formation of C(sp3)–heteroatom bonds

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Окт. 8, 2022

Abstract Sterically congested C–O and C–N bonds are ubiquitous in natural products, pharmaceuticals, bioactive compounds. However, the development of a general method for efficient construction those sterically demanding covalent still remains formidable challenge. Herein, photoredox-driven ring-opening C( sp 3 )–heteroatom bond formation arylcyclopropanes is presented, which enables structurally diversified while dialkyl ether, alkyl ester, alcohol, amine, chloride/fluoride, azide also thiocyanate derivatives. The selective single electron oxidation aryl motif associated with thermodynamic driving force from ring strain-release key this transformation. By synergistic activation mode, C–C cleavage otherwise inert cyclopropane framework successfully unlocked. Further mechanistic computational studies disclose complete stereoinversion upon nucleophilic attack, thus proving concerted S N 2-type functionalization manifold, regioselectivity subjected to an orbital control scenario.

Язык: Английский

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Recent Advances in Transition-Metal-Catalyzed Cross-Coupling Reactions of gem-Difluorinated Cyclopropanes

Synlett, Год журнала: 2022, Номер 34(01), С. 1 - 13

Опубликована: Июль 28, 2022

Abstract As a special class of cyclopropanes, gem-difluorinated cyclopropanes have many fascinating properties as result the gem-difluoro substitution; thus, their reactions received much attention from synthetic chemistry community. Recently, gradually emerged type novel and unique fluorinated allylic synthon in cross-coupling for synthesis monofluoroalkenes. Herein, we briefly summarize recent advances transition-metal-catalyzed cyclopropanes. 1 Introduction 2 Palladium-Catalyzed Reactions with Linear Selectivity 3 Branched 4 Other Metal-Catalyzed 5 Conclusions

Язык: Английский

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Pd/IPr^BIDEA-Catalyzed Hydrodefluorination of gem-Difluorocyclopropanes: Regioselective Synthesis of Terminal Fluoroalkenes

Journal of the American Chemical Society, Год журнала: 2023, Номер 146(1), С. 24 - 32

Опубликована: Окт. 13, 2023

Developing new strategies to enable chemo- and regioselective reductions is an important topic in chemical research. Herein, efficient Pd/IPr

Язык: Английский

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Palladium‐Catalyzed Fluorinative Bifunctionalization of Aziridines and Azetidines with gem‐Difluorocyclopropanes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(42)

Опубликована: Авг. 12, 2023

Abstract An unprecedented Pd‐catalyzed fluorinative bifunctionalization of aziridines and azetidines was successfully developed via regioselective C−C C−F bond cleavage gem‐difluorocyclopropanes, leading to various β,β′‐bisfluorinated amines β,γ‐bisfluorinated amines. This reaction achieved by incorporating a 2‐fluorinated allyl group fluorine atom scissored from gem‐difluorocyclopropane in 100 % economy for the first time. The mechanistic investigations indicated that underwent amine attacking palladium complex generate η 2 ‐coordinated N‐allyl aziridine followed fluoride ligand transfer affording final β‐ γ‐fluorinated

Язык: Английский

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Selectivity in Rh-catalysis with gem-difluorinated cyclopropanes

Chemical Communications, Год журнала: 2024, Номер 60(28), С. 3764 - 3773

Опубликована: Янв. 1, 2024

This feature article summarizes our efforts towards developing Rh-catalyzed reactions of gem -difluorinated cyclopropanes, briefly discussing the design, selectivity, mechanisms and future research prospects.

Язык: Английский

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