Geminal dimetalation of alkylidene-type carbenoids with silylboranes and diborons

Kurahashi, Takuya; Hata, Takeshi; Masai, Hirokazu; Kitagawa, Hirotoshi; Shimizu, Masaki; Hiyama, Tamejiro

doi:10.1016/s0040-4020(02)00648-8

Cited by 123 publications

(46 citation statements)

References 66 publications

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“…The process of generation of alkylidene‐type carbenoids by deprotonation, gem ‐silylborylation or gem ‐diborylation, involving lithium 2,2,6,6‐tetramethylpiperidide (LiTMP) or BuLi is an effective method for the synthesis of dienes with one or two borane groups attached to C

_{sp^{2}}

atom in C=C fragment at the terminal position 6 , 8 , 11 , 12 (Scheme , Path I and Path II) . The essence of the gem ‐dimetalation, for example gem ‐silylborylation of carbenoids pathway, is the borate complex B possessing silicon atom as a migrating group, which leads the product C with inversion of the configuration (Scheme ).…”

Section: Preparation Of Boron‐substituted 13‐dienesmentioning

confidence: 99%

Recent Advances in Boron‐Substituted 1,3‐Dienes Chemistry: Synthesis and Application

Pyziak

Walkowiak

Marciniec

2016

Chemistry A European J

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In the syntheses developed to access naturally occurring compounds, especially bioactive substances, boron-functionalized dienes (also "linchpin" reagents) are used as key reagents. Structurally unique dienes are found in nature, and play important biological and chemical roles. Recently, linchpin moieties have been proved as useful substrates for a variety of highly functionalized chemical transformations. The products of these processes are potentially of some use for the syntheses of an important class of natural products showing a wide range of biological activities. This review describes progress in the synthesis of borylsubstituted buta-1,3-dienes as well as their application in organic chemistry.

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_{sp^{2}}

Section: Preparation Of Boron‐substituted 13‐dienesmentioning

confidence: 99%

Recent Advances in Boron‐Substituted 1,3‐Dienes Chemistry: Synthesis and Application

Pyziak

Walkowiak

Marciniec

2016

Chemistry A European J

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“…(1)] Although a variety of the vic-hetero-dimetallated alkenes can be synthesized by transition-metal-catalyzed direct insertion reactions of alkynes [1][2][3][4] into metal-metal (MÀM') bonds, the search for new synthetic approaches is still of great importance. [9] We have recently reported efficacious access to vic-diborylalkenes by the copper-catalyzed diborylation of alkynes with a diboron in which b-borylalkenyl-copper species serve as key intermediates. [10,11] In view of the nucleophilicity of organocopper species, [12] we envisaged that b-borylalkenyl-copper species could also be key intermediates in a new type of borylmetalation reactions by capturing with metallic electrophiles.…”

Section: Introductionmentioning

confidence: 99%

Copper‐Catalyzed Three‐Component Borylstannylation of Alkynes

Takemoto

Yoshida

Takaki

2012

Chemistry A European J

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Regio- and stereoselective installation of boryl and stannyl moieties into a carbon-carbon triple bond of various alkynes has been achieved based on a three-component coupling reaction by using a diboron and a tin alkoxide with the aid of a copper(II) acetate-tricyclohexylphosphine complex, giving diverse vic-borylstannylalkenes in a straightforward manner. Carbon-tin and carbon-boron bonds of the resulting borylstannylation product are successively transformed into carbon-carbon bonds by a Migita-Kosugi-Stille and a Suzuki-Miyaura coupling, leading to the formation of (Z)-tamoxifen with anti-breast cancer activity.

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“…Silaboration was found to take place regio‐ and stereoselectively, with the silyl moiety geminal to the phenyl group. Although similar 1,1‐diboryl‐1‐alkenes have been prepared by gem ‐diborylation of 1,1‐dibromo‐1‐alkenes with n ‐BuLi/bis(pinacolato)diboron67,68 or ketone addition of tris(pinacolato)borylmethyllithium,69 there are no published examples of silylated 1,1‐diboryl‐1‐alkenes, which are difficult to synthesize under basic conditions due to the occurrence of desilylation. A possible catalytic cycle forming 3 is proposed to explain the observed regioselectivity, which is presented in Scheme .…”

Section: Silaboration Of An Alkynylboronatementioning

confidence: 99%

Synthesis of Multisubstituted Olefins through Regio‐ and Stereoselective Addition of Interelement Compounds Having B–Si, B–B, and Cl–S Bonds to Alkynes, and Subsequent Cross‐Couplings

Iwasaki¹,

Nishihara²

2016

The Chemical Record

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Multisubstituted olefins are fundamental motifs in organic compounds. In this account, we describe the synthesis of organic molecules bearing an olefinic moiety by the transition-metal-catalyzed regio- and stereoselective addition of a variety of interelement compounds to alkynes. Regio- and stereoselective silaboration, diborylation, and chlorothiolation have been achieved by using the transition-metal catalysts. The subsequent cross-coupling reactions of the boron-containing alkenes to install various aryl groups afforded the corresponding tri- and tetraarylated olefins. This account describes our research on the highly regio- and stereoselective synthesis of multifunctionalized olefins such as tetraarylethenes with four different aryl groups.

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Geminal dimetalation of alkylidene-type carbenoids with silylboranes and diborons

Cited by 123 publications

References 66 publications

Recent Advances in Boron‐Substituted 1,3‐Dienes Chemistry: Synthesis and Application

Recent Advances in Boron‐Substituted 1,3‐Dienes Chemistry: Synthesis and Application

Copper‐Catalyzed Three‐Component Borylstannylation of Alkynes

Synthesis of Multisubstituted Olefins through Regio‐ and Stereoselective Addition of Interelement Compounds Having B–Si, B–B, and Cl–S Bonds to Alkynes, and Subsequent Cross‐Couplings

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