Additive- and Metal-Free, Predictably 1,2- and 1,3-Regioselective, Photoinduced Dual C–H/C–X Borylation of Haloarenes

Mfuh, Adelphe; Nguyen, Vu Tuan; Chhetri, Bhuwan; Burch, Jessica; Doyle, John; Нестеров, В. Н.; Arman, Hadi D.; Larionov, Oleg V.

doi:10.1021/jacs.6b05436

Cited by 114 publications

(49 citation statements)

References 81 publications

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“…[6] However,a ll these valuable methods require at ransition metal catalyst, al igand and as toichiometric amount of ab ase.T oo ur knowledge,m etal and additive-free radical borylation of alkyl halides with diborons is unknown. [7] Arylboronates can be obtained from haloarenes and diborons via reactive aryl radicals [8][9][10][11][12][13] (Scheme 1B). Along these lines,Marder developed azinc(II)-catalyzed borylation of aryl halides using astoichiometric base [8] and photoinduced aryl halide borylation was reported by Larionov, [9] Li [10] and Fu.…”

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confidence: 99%

“…[7] Arylboronates can be obtained from haloarenes and diborons via reactive aryl radicals [8][9][10][11][12][13] (Scheme 1B). Along these lines,Marder developed azinc(II)-catalyzed borylation of aryl halides using astoichiometric base [8] and photoinduced aryl halide borylation was reported by Larionov, [9] Li [10] and Fu. [11] Recently,apyridine-catalyzed radical borylation of aryl halides was disclosed by Jiao.…”

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confidence: 99%

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Metal‐Free Radical Borylation of Alkyl and Aryl Iodides

2018

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A metal‐free radical borylation of alkyl and aryl iodides with bis(catecholato)diboron (B 2 cat 2 ) as the boron source under mild conditions is introduced. The borylation reaction is operationally easy to conduct and shows high functional group tolerance and broad substrate scope. Radical clock experiments and density functional theory calculations provide insights into the mechanism and rate constants for C‐radical borylation with B 2 cat 2 are disclosed.

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Metal‐Free Radical Borylation of Alkyl and Aryl Iodides

2018

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“…A similar photoinduced borylation method was also developed by Li 30,31 . We also showed that a 1,2- and 1,3-regioselective dual C–H/C–X borylation of haloarenes can be achieved on preparative scale 32 (Fig. 1d).…”

Section: Introductionmentioning

confidence: 61%

Metal- and additive-free photoinduced borylation of haloarenes

et al. 2017

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Boronic acids and esters have crucial roles in the areas of synthetic organic chemistry, molecular sensors, materials science, drug discovery, and catalysis. Many of the current applications of boronic acids and esters require materials with very low levels of transition metal contamination. Most of the current methods for the synthesis of boronic acids require, however, transition metal catalysts and ligands that have to be removed via additional purification procedures. This protocol describes a simple, metal- and additive-free method of conversion of haloarenes directly to boronic acids and esters. This photoinduced borylation protocol does not require expensive and toxic metal catalysts and ligands and produces innocuous and easy-to-remove by-products. Furthermore, the reaction can be carried out on multigram scales in common grade solvents without the need for reaction mixtures to be deoxygenated. The setup and purification steps are typically accomplished within 1–3 h. The reactions can be run overnight, and the protocol can be completed within 13–16 h. Two representative procedures that are described in this protocol provide details for preparation of a boronic acid (3-cyanopheylboronic acid) and a boronic ester (1,-benzenediboronic acid bis(pinacol)ester). We also discuss additional details of the method that will be helpful in the application of the protocol to other haloarene substrates.

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“…In 2016, Larionov and co‐workers developed an unprecedented photoinduced dual C–H/C−X borylation of haloarenes 152 with B 2 Pin 2 as the borylation source under mild conditions (Scheme ) . A variety of 1,2‐ ( 153 ) and 1,3‐ ( 154 ) diborylarenes have been achieved regioselectively in good to excellent yields from chloro‐, bromo‐, and iodo‐arenes.…”

Section: Miscellaneous Reactionsmentioning

confidence: 99%

“…In 2016, Larionov and co-workers developed an unprecedented photoinduced dual C-H/CÀ X borylation of haloarenes 152 with B 2 Pin 2 as the borylation source under mild conditions (Scheme 46). [74] A variety of 1,2-(153) and 1,3-Scheme 43. Knoevenagel-type reaction involved annulation to access tetrasubstituted thiophenes.…”

Section: Photoinduced Borylation Reactionsmentioning

confidence: 99%

Fluorinated Alcohols: Magic Reaction Medium and Promoters for Organic Synthesis

Xiao

2019

The Chemical Record

110

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Fluorinated alcohols have been widely used in the synthetic organic chemistry over the past decades. The unique properties such as the strong hydrogen‐bonding donor ability and low nucleophilicity allow them to promote organic reactions in the absence of any catalyst. These approaches have distinct advantages in terms of operational simplicity, practicability and environmental friendliness. Reactions promoted by fluorinated alcohols, including nucleophilic substitution reactions, annulation reactions, electrophilic reactions, dearomatization reactions, functionalization of multiple bond, epoxidation reactions and miscellaneous reactions have been summarized in this account.

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Additive- and Metal-Free, Predictably 1,2- and 1,3-Regioselective, Photoinduced Dual C–H/C–X Borylation of Haloarenes

Cited by 114 publications

References 81 publications

Metal‐Free Radical Borylation of Alkyl and Aryl Iodides

Metal‐Free Radical Borylation of Alkyl and Aryl Iodides

Metal- and additive-free photoinduced borylation of haloarenes

Fluorinated Alcohols: Magic Reaction Medium and Promoters for Organic Synthesis

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