An Olefinic 1,<scp>2‐<i>α</i>‐Boryl</scp> Migration Enables 1,<scp>2‐Bis</scp>(boronic esters) via <scp>Radical‐Polar</scp> Crossover Reaction

Zhang, Feng; Liao, Shangteng; Zhou, Lu; Yang, Kai; Wang, Chenglan; Lou, Yixian; Wang, Cece; Song, Qiuling

doi:10.1002/cjoc.202100701

Cited by 24 publications

(8 citation statements)

References 50 publications

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“…These protocols, featuring broad scope and high yields, provided direct access to fluoroalkylated vicinal diborylalkanes, which were typically oxidized to their corresponding diols in a one pot approach. [171] From a mechanistic perspective, the Pd-catalyzed carbofluoroalkylation is a radical process, confirmed by trapping [164][165][166][167][168] and radical clock [164] experiments. However, there has been some debate in the mechanistic picture of the overall process.…”

Section: Carbofluoroalkylationsmentioning

confidence: 95%

“…This strategy was utilized for the fluoroalkylation of vinyldiboronate complexes formed from an alkenylmagnesium reagent and gem ‐diborylalkanes under Ru‐photocatalysis. These protocols, featuring broad scope and high yields, provided direct access to fluoroalkylated vicinal diborylalkanes, which were typically oxidized to their corresponding diols in a one pot approach [171] …”

Section: Multicomponent Reactionsmentioning

confidence: 99%

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Fluoroalkyl Iodides in Fluoroalkylative Difunctionalization of C−C Multiple Bonds

Lucio‐Martínez

Chaładaj

2023

Adv Synth Catal

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Fluorinated alkyl iodides serve as a convenient and inexpensive source of fluoroalkyl radicals that can readily undergo addition to the CÀ C unsaturated bonds of alkynes and alkenes which is the foundation for a variety of useful synthetic protocols. Since 2010 this field has witnessed huge progress in several respects. First the portfolio of fluorinated alkyl iodides was extended beyond only simple perfluoroalkyl iodides (C n F 2n + 1 I). In particular, employment of iododifluoroÀ methyl-carbonyls and phosphonates has enabled facile installation of the medicinally relevant difluoromethylene motif. Secondly, from a conceptual point of view, novel strategies for activation of fluoroalkyl iodides towards radical formation have been introduced, relying on the formation of electron donor-acceptor (EDA) complexes, photoredox catalysis, frustrated Lewis pairs and transition metal catalysis, complementing prior approaches based on heat and UV induced CÀ I homolysis, radical initiators, and simple electron transfer processes. Based on these strategies a range of novel fluoroalkylative transformations of unsaturated systems have been added to classical iodoperfluoroalkylation. Broadly applicable protocols for simple fluoroalkylation and hydrofluoroalkylation, as well as for more sophisticated, complexitybuilding methods of fluoroalkylation-annulation and tandem multicomponent fluoroalkylations with concomitant installation of another functionality have been recently disclosed. This review summarizes the progress achieved since 2010 in the reactivity of fluoroalkyl iodides towards alkenes and alkynes with emphasis placed on the above-mentioned advances.1.

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Section: Carbofluoroalkylationsmentioning

confidence: 95%

Section: Multicomponent Reactionsmentioning

confidence: 99%

Fluoroalkyl Iodides in Fluoroalkylative Difunctionalization of C−C Multiple Bonds

Lucio‐Martínez

Chaładaj

2023

Adv Synth Catal

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“…[20] Favoured by the lack of stabilization of the tetracoordinated α-boryl radicals, four-coordinate alkenylboronic esters were found to undergo efficient ATRA. [21][22][23][24][25][26] In a related manner, [11,[27][28][29] ATRA processes involving electrophilic radicals and ate-complexes of vinylboronic pinacol ester [30] and diverse organolithium (or organomagnesium) species have been used for an attractive three-component coupling process involving a subsequent 1,2-metallate shifts of carbon [25,[31][32][33][34][35][36][37][38][39][40][41] and boryl nucleophiles. [42] Nucleophilic radicals also add efficiently to vinylboronic esters as demonstrated by Carboni.…”

Section: Introductionmentioning

confidence: 99%

Borylated Cyclopentanes via Atom Transfer Radical [3+2] Annulation

Cirule,

Dénès,

Gnägi‐Lux

et al. 2024

Adv Synth Catal

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Abstract. An atom transfer radical [3+2] annulation (ATRAn) reaction involving alkenyl boronic esters and homoallylic iodides provides a rapid access to polysubstituted borylated cyclopentanes. A variety of α‐substituted vinylboronic esters are suitable substrates and offer unique opportunities for further modification of the formed 5‐membered ring. For instance, the oxidation of the boronic ester to an alcohol allows the preparation of products that corresponds to an annulation involving the enol form of acetone. Substitution of the iodide by a nucleophile such as lithium methoxide without modifying the boronic ester moiety is also feasible. Finally, by using a (3‐acetoxyprop‐1‐en‐2‐yl)boronic ester, a facile 1,2‐elimination reaction provided a methylenecyclopentane. In this case, the alkenylboronate radical trap acts as an equivalent to allene, a building block so far elusive for preparative radical reactions.

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“…Tetracoordinate boron complexes as key intermediates are widely existing in boron-involved transformations, and the common reaction modes for tetracoordinate boron species are 1,2-metalate migration reactions as well as transformation in coupling reactions . Very recently, tetracoordinate boron species as alkyl radical precursors have emerged and been successfully applied to transition-metal-catalyzed coupling reactions .…”

mentioning

confidence: 99%

Synthesis of α-Haloboronates by the Halogenation of gem-Diborylalkanes via Tetracoordinate Boron Species

Liao

Liang

et al. 2023

Org. Lett.

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α-Haloboronates have a wide range of applications in organic chemistry as synthetic synthons; however, traditional synthetic methods of α-haloboronates are harsh and complicated. Herein, we used n BuLi as the nucleophilic reagent to attack the boron atom in gem-diborylalkanes to form tetracoordinate boron species and successfully achieved α-chloroboronates and αbromoboronates with readily accessible electrophilic halogen reagents (NCS and NBS). The reaction is transition-metal-free and features a broad substrate scope and diversified valuable products.

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An Olefinic 1,2‐α‐Boryl Migration Enables 1,2‐Bis(boronic esters) via Radical‐Polar Crossover Reaction

Cited by 24 publications

References 50 publications

Fluoroalkyl Iodides in Fluoroalkylative Difunctionalization of C−C Multiple Bonds

Fluoroalkyl Iodides in Fluoroalkylative Difunctionalization of C−C Multiple Bonds

Borylated Cyclopentanes via Atom Transfer Radical [3+2] Annulation

Synthesis of α-Haloboronates by the Halogenation of gem-Diborylalkanes via Tetracoordinate Boron Species

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