Radical Addition of <i>α</i>-Halo Ester to Homoallylic Gallium or Indium Species: Formation of Cyclopropane Derivatives

Usugi, Shin‐ichi; Tsuritani, Takayuki; Yorimitsu, Hideki; Shinokubo, Hiroshi; Oshima, Koichiro

doi:10.1246/bcsj.75.841

Cited by 20 publications

(10 citation statements)

References 18 publications

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“…Oshima et al have reported a radical reaction of α-halo carbonyl compounds with the butenylindium species prepared by transmetalation between 3-butenylmagnesium bromide (4) and indium halide. [15] However, application to the coupling with 2a failed, and most of the unreacted 2a was recovered (Scheme 2). The low yield was probably caused by the magnesium salt (MgBr 2 ) generated in situ.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Cyclopropane‐Containing Phosphorus Compounds by Radical Coupling of Butenylindium with Iodo Phosphorus Compounds

et al. 2011

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The radical coupling of α-or β-iodo phosphorus compounds such as iodo phosphonate, iodo phosphane oxide, and iodo phosphonothioate with butenylindium species, prepared by transmetalation between a (cyclopropylmethyl)stannane and InBr 3 , afforded the corresponding cyclopropylmethylated products. The radical reaction was initiated by the radical species generated from butenylindium assisted by a small amount of oxygen. Butenylindium works not only as a cyclopropylmethylating reagent, but also as a radical initiator. For

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Section: Resultsmentioning

confidence: 99%

Synthesis of Cyclopropane‐Containing Phosphorus Compounds by Radical Coupling of Butenylindium with Iodo Phosphorus Compounds

et al. 2011

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“…Reactive organolithium and organomagnesium compounds undergo transmetalation generally at room temperature. Examples are allyl-, 20 vinyl-, 21 alkynyl-, 22 3-butenylmagnesium halides, 23 lithium acetylides, 24 lithiated phenols, 25 and lithiated anilines 26 (Scheme 9).…”

Section: Transmetalationmentioning

confidence: 99%

Trichlorogallium and trialkylgalliums in organic synthesis

Yamaguchi

Nishimura

2008

Chem. Commun.

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“…Bond formation at the less substituted carbon yields the 3-iodoalkylgallium via atom-transfer addition; the organogallium intermediate then undergoes intramolecular cyclization to form the cyclopropane ring. 22 The reaction mechanism of the allylation, especially the fate of the g-gallylalkyl radical intermediate 5, is not clear. Scheme 3 illustrates two plausible mechanisms, in the absence of water for clarity, which involve: (1) elimination of divalent gallium radical from 5 (Path A); or (2) halogen atom abstraction of 5 from a-halo carbonyl compound 1 (Path B).…”

Section: Biographical Sketchesmentioning

confidence: 99%

Radical Allylation, Vinylation, Alkynylation, and Phenylation Reactions of α-Halo Carbonyl Compounds with Organoboron, Organogallium, and Organoindium Reagents

Takami¹,

Usugi²,

Yorimitsu³

et al. 2005

Synthesis

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Allylic gallium and indium reagents are found to mediate radical allylation reactions of a-iodo or a-bromo carbonyl compounds. Treatment of benzyl bromoacetate with allylgallium, prepared from allylmagnesium chloride and gallium trichloride, in the presence of triethylborane provided benzyl 4-pentenoate in excellent yield. Addition of water as a co-solvent improved the yields of allylated products. Allylic indium reagents are also useful and can replace the gallium reagents. A diallylborane reagent can allylate an a-iodo ester in good yield. Alkenylation reactions of a-halo carbonyl compounds with alkenylindium proceeded via a radical process in the presence of triethylborane. Unactivated alkene moieties and styryl groups were introduced by this method. The carbon-carbon double bond geometry of the alkenylindiums was retained during the alkenylation. Preparation of an alkenylindium via a hydroindation of 1-alkyne and subsequent radical alkenylation established an efficient one-pot strategy. Radical alkynylations and phenylations with organoindium reagents are disclosed herein.

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Radical Addition of α-Halo Ester to Homoallylic Gallium or Indium Species: Formation of Cyclopropane Derivatives

Cited by 20 publications

References 18 publications

Synthesis of Cyclopropane‐Containing Phosphorus Compounds by Radical Coupling of Butenylindium with Iodo Phosphorus Compounds

Synthesis of Cyclopropane‐Containing Phosphorus Compounds by Radical Coupling of Butenylindium with Iodo Phosphorus Compounds

Trichlorogallium and trialkylgalliums in organic synthesis

Radical Allylation, Vinylation, Alkynylation, and Phenylation Reactions of α-Halo Carbonyl Compounds with Organoboron, Organogallium, and Organoindium Reagents

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