Saturated Boronic Acids, Boronates, and Trifluoroborates: An Update on Their Synthetic and Medicinal Chemistry DOI
Dmitriy M. Volochnyuk, Alina O. Gorlova, Oleksandr O. Grygorenko

et al.

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(62), P. 15277 - 15326

Published: Sept. 9, 2021

Abstract This review discusses recent advances in the chemistry of saturated boronic acids, boronates, and trifluoroborates. Applications title compounds design boron‐containing drugs are surveyed, with special emphasis on α‐amino derivatives. A general overview as modern tools to construct C(sp 3 )−C )‐heteroatom bonds is given, including developments Suzuki‐Miyaura Chan‐Lam cross‐couplings, single‐electron‐transfer processes metallo‐ organocatalytic photoredox reactions, transformations boron “ate” complexes. Finally, an attempt summarize current state art synthesis trifluoroborates made, a brief mention “classical” methods (transmetallation organolithium/magnesium reagents species, anti‐Markovnikov hydroboration alkenes, modification alkenyl compounds) focus methodologies (boronation alkyl (pseudo)halides, derivatives carboxylic alcohols, primary amines, boronative C−H activation, novel approaches alkene hydroboration, 1,2‐metallate‐type rearrangements).

Language: Английский

Photocatalytic C(sp3) radical generationviaC–H, C–C, and C–X bond cleavage DOI Creative Commons
Chia‐Yu Huang, Jianbin Li, Chao‐Jun Li

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(19), P. 5465 - 5504

Published: Jan. 1, 2022

C(sp 3 ) radicals (R˙) are of broad research interest and synthetic utility.

Language: Английский

Citations

77
New avenues for C–B bond formationviaradical intermediates DOI Creative Commons

Florian W. Friese,

Armido Studer

Chemical Science, Journal Year: 2019, Volume and Issue: 10(37), P. 8503 - 8518

Published: Jan. 1, 2019

Efficient radical routes to important alkyl and aryl boronic esters have been developed over the past few years. Such reactions are complementary existing transition-metal catalysed cross coupling processes.

Language: Английский

Citations

142
Dynamic Kinetic Cross-Electrophile Arylation of Benzyl Alcohols by Nickel Catalysis DOI
Peng Guo, Ke Wang,

Wen-Jie Jin

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 143(1), P. 513 - 523

Published: Dec. 28, 2020

Catalytic transformation of alcohols via metal-catalyzed cross-coupling reactions is very important, but it typically relies on a multistep procedure. We here report dynamic kinetic approach for the direct functionalization alcohols. The feasibility this strategy demonstrated by nickel-catalyzed cross-electrophile arylation reaction benzyl with (hetero)aryl electrophiles. proceeds broad substrate scope both coupling partners. electron-rich, electron-poor, and ortho-/meta-/para-substituted electrophiles (e.g., Ar–OTf, Ar–I, Ar–Br, inert Ar–Cl) all coupled well. Most functionalities, including aldehyde, ketone, amide, ester, nitrile, sulfone, furan, thiophene, benzothiophene, pyridine, quinolone, Ar–SiMe3, Ar–Bpin, Ar–SnBu3, were tolerated. nature method enables benzylic alcohol in presence various nucleophilic groups, nonactivated primary/secondary/tertiary alcohols, phenols, free indoles. It thus offers robust alternative to existing methods precise construction diarylmethanes. synthetic utility was concise synthesis biologically active molecules its application peptide modification conjugation. Preliminary mechanistic studies revealed that situ formed oxalates nickel, possibly radical process, an initial step aryl

Language: Английский

Citations

140
Site‐Selective 1,2‐Dicarbofunctionalization of Vinyl Boronates through Dual Catalysis DOI
Shang‐Zheng Sun, Yaya Duan, Riccardo S. Mega

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(11), P. 4370 - 4374

Published: Jan. 7, 2020

A modular, site-selective 1,2-dicarbofunctionalization of vinyl boronates with organic halides through dual catalysis is described. This reaction proceeds under mild conditions and characterized by excellent chemo- regioselectivity. It thus represents a complementary new technique for preparing densely functionalized alkyl boron architectures from simple accessible precursors.

Language: Английский

Citations

139
Photoinduced Deoxygenative Borylations of Aliphatic Alcohols DOI
Jingjing Wu, Robin M. Bär, Lin Guo

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(52), P. 18830 - 18834

Published: Oct. 15, 2019

A photochemical method for converting aliphatic alcohols into boronic esters is described. Preactivation of the alcohol as a 2-iodophenyl-thionocarbonate enables novel Barton-McCombie-type radical deoxygenation that proceeds efficiently with visible light irradiation and without requirement photocatalyst, initiator, or tin silicon hydrides. The resultant alkyl intercepted by bis(catecholato)diboron, furnishing from diverse range structurally complex alcohols.

Language: Английский

Citations

131
Radical Dehydroxylative Alkylation of Tertiary Alcohols by Ti Catalysis DOI
Hao Xie, Jiandong Guo, Yuquan Wang

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(39), P. 16787 - 16794

Published: Sept. 4, 2020

Deoxygenative radical C–C bond-forming reactions of alcohols are a long-standing challenge in synthetic chemistry, and the current methods rely on multistep procedures. Herein, we report direct dehydroxylative alkylation reaction tertiary alcohols. This new protocol shows feasibility generating carbon radicals from offers an approach for facile precise construction all-carbon quaternary centers. The proceeds with broad substrate scope activated alkenes. It can tolerate wide range electrophilic coupling partners, including allylic carboxylates, aryl vinyl electrophiles, primary alkyl chlorides/bromides, making method complementary to cross-coupling is highly selective alcohols, leaving secondary/primary (benzyl included) phenols intact. utility highlighted by its 10-g-scale late-stage modification complex molecules. A combination experiments density functional theory calculations establishes plausible mechanism implicating generated via Ti-catalyzed homolysis C–OH bond.

Language: Английский

Citations

126
Silaboration of [1.1.1]Propellane: A Storable Feedstock for Bicyclo[1.1.1]pentane Derivatives DOI
Masaki Kondo, Junichiro Kanazawa, Tomohiro Ichikawa

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(5), P. 1970 - 1974

Published: Oct. 11, 2019

The silaboration of [1.1.1]propellane enables direct introduction B and Si functional groups onto the bicyclo[1.1.1]pentane (BCP) scaffold in high yield under mild, additive-free conditions. silaborated BCP can be obtained on a gram-scale single step without need for column-chromatographic purification, is storable easy to handle, providing versatile synthetic intermediate derivatives. We also describe various conversions C-B/C-Si bonds scaffold, including development modified Suzuki-Miyaura cross-coupling reaction at highly sterically hindered bridgehead sp3 carbon center skeleton using combination activated boronic esters, copper(I) oxide, PdCl2 (dppf) catalyst system.

Language: Английский

Citations

121
Dual Catalytic Strategy for Forging sp2–sp3and sp3–sp3Architectures via β-Scission of Aliphatic Alcohol Derivatives DOI
Fei Cong, Xin‐Yang Lv, Craig S. Day

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(49), P. 20594 - 20599

Published: Nov. 30, 2020

A dual platform for forging sp2-sp3 and sp3-sp3 carbon bonds via catalytic β-scission of aliphatic alcohol derivatives with both aryl alkyl halides is disclosed. This protocol distinguished by its wide substrate scope broad applicability, even in the context late-stage functionalization.

Language: Английский

Citations

106
Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances DOI
Oleksandr O. Grygorenko, Dmitriy M. Volochnyuk, Bohdan V. Vashchenko

et al.

European Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 2021(47), P. 6478 - 6510

Published: Sept. 8, 2021

Abstract Current medicinal chemistry relies heavily on the quality of building blocks, i. e. reagents used to introduce chemical diversity into target molecules. The last decade witnessed an emergence many novel (or well‐overlooked old) chemotypes for drug discovery, which is related adapting new synthetic methodologies, designing sp 3 ‐enriched bioisosteres, paying attention previously underrated even unwanted) structural motifs, or combination thereof. In this review with 532 references, a survey selected that emerged recently in provided, focus synthesis corresponding blocks. Thus, saturated (hetero)aliphatic boronates, sulfonyl fluorides, sulfinates, non‐classical benzene isosteres, bicyclic morpholine/piperidine/piperazine analogs, as well gem ‐difluorinated cycloalkanes (as example emerging fluorinated motifs) are discussed.

Language: Английский

Citations

96
Boryl Radical Addition to Multiple Bonds in Organic Synthesis DOI
Tsuyoshi Taniguchi

European Journal of Organic Chemistry, Journal Year: 2019, Volume and Issue: 2019(37), P. 6308 - 6319

Published: Aug. 9, 2019

Boryl radicals have recently contributed to the development of organoboron chemistry, but synthetic application boryl is still limited compared with other radical species. The recent new reagents and catalytic systems has expanded practicality in it enabled addition reactions multiple bonds such as alkenes, alkynes, carbonyl groups their derivatives. additions can create not only novel compounds also unusual chemical transformations. This review summarizes developed radicals, which are roughly categorized by strategy for formation radicals: (1) B–H bond cleavage (2) B–B cleavage. Also, reaction mechanism outlined order understand design concept each reaction.

Language: Английский

Citations

88