Regioselective Markovnikov Hydrochalcogenation of Terminal Alkynes with Indium(III) Benzenechalcogenolates

Peppe, Clóvis; Castro, Lierson Borges de; Mello, Melina de Azevedo; Barros, Olga Soares do Rego

doi:10.1055/s-2008-1072725

Cited by 15 publications

(7 citation statements)

References 4 publications

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“…In addition to the above propargylic alcohols, propargylic amine can be used as well (Scheme ) . However, only tri(phenylseleno)indium [(PhSe) 3 In], generated from the insertion of indium into diphenyl diselenides, was reactive enough to undergo the addition reaction.…”

Section: (Organothio)indium and (Organoseleno)indium Reagentmentioning

confidence: 99%

“…805 In addition to the above propargylic alcohols, propargylic amine can be used as well (Scheme 588). 806 solvent (Scheme 589). 807 Interestingly, the vinyl selenide adduct could isomerize to the corresponding internal vinyl selenide upon prolonging the reaction time to 48 h. The internal vinyl selenide formed can be further transformed into the corresponding ketone upon refluxing in the presence of InBr 3 .…”

Section: Application In Organic Synthesismentioning

confidence: 99%

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Organoindium Reagents: The Preparation and Application in Organic Synthesis

et al. 2012

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allylation performed in aqueous media, an efficient synthesis of highly functionalized lactones was realized in good yields (64− 77%, Scheme 29). 238 However, the chirality installed during the first step almost had no influence on the second step, thus resulting in poor diastereoselectivity in the subsequent allylation reaction (1:1−2:1 dr).In situ formation of aldehyde from the oxidation of alcohol followed by one-pot indium-mediated allylation also provides an alternative method for the synthesis of homoallylic alcohol. Recently, Yadav and co-workers developed such a one-pot sequence by using chloramines-T (sodium salt of Nchlorotosylamide) as oxidant in the presence of a catalytic amount of FeCl 3 in CH 2 Cl 2 , giving rise to homoallylic alcohols in good to excellent yields (Scheme 30). 239 It is noteworthy that the generated byproduct of TsNH 2 (from the reduction of chloramines-T) may react with the in situ-formed aldehydes to give intermediates of N-tosylimines in the presence of 4 Å molecular sieve under refluxing; the thus-formed N-tosylimines subsequently underwent one-pot indium-mediated allylation to produce homoallylic amines in 60−80% yields. Later, a similar one-pot, two-step sequence for the synthesis of homoallylic alcohols via a galactose oxidase-mediated chemo-enzymatic oxidation of benzyl and cinnamyl alcohols to the corresponding Scheme 23 Scheme 24 Scheme 25 Scheme 26 Scheme 27 Scheme 28 Scheme 29 Scheme 30 Chemical Reviews Review dx.

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Section: (Organothio)indium and (Organoseleno)indium Reagentmentioning

confidence: 99%

Section: Application In Organic Synthesismentioning

confidence: 99%

Organoindium Reagents: The Preparation and Application in Organic Synthesis

et al. 2012

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“…Indium(I) iodide is found to promote the regio-and stereoselective hydrothiolation of propargyl alcohols with (PhSe) 2 (Markovnikov-type addition and anti-addition) [96]. In addition, regioselective Markovnikov hydroselenation of terminal alkynes using indium(III) selenates is also reported [97]. The Pd(OAc) 2 -catalyzed hydroselenation of alkynes with PhSeH can be applied to the hydroselenation of allenes [98].…”

Section: Hydrothiolation Of Allenesmentioning

confidence: 96%

Transition-Metal-Catalyzed S–H and Se–H Bonds Addition to Unsaturated Molecules

Ogawa

2011

Hydrofunctionalization

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This chapter deals with the transition-metal-catalyzed hydrothiolation and hydroselenation of alkynes and allenes and related unsaturated compounds with thiols and selenols. In these reactions, the regio-and/or stereoselectivities of the addition products can be controlled by switching the transition metal catalysts. Metal sulfides and selenides (RE-ML n , E ¼ S, Se, M ¼ Ni, Pd, Rh, Zr, Sm, etc.) play an important role as key catalyst species in these hydrothiolation and hydroselenation. The introduction of carbon monoxide into these hydrothiolation and hydroselenation systems leads to novel carbonylation with simultaneous addition of thio and seleno groups to unsaturated bonds.

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“…Indium(III) chalcogenolates obtained from indium monohalides and diphenyl dichalcogenides [22] have been extensively applied in organic synthesis to generate carbon-chalcogen bonds. Reactions of interest include: ring opening reactions of epoxides with IIn(EPh) 2 (E = S, Se) to the corresponding b-hydroxy selenides [23] and sulfides [24], ring opening reactions of aziridines with IIn(SePh) 2 to selenocysteine derivatives and selenotreonine [25], hydrochalcogenation of terminal alkynes, alkynols and aminoalkynes with XIn(EPh) 2 (X = Br, I; E = S, Se, Te] [26][27][28][29], Pd(0) catalyzed coupling between IIn(EPh) 2 (E = S, Se) with vinyl bromides to vinylic chalcogenides [30], condensations of IIn(EPh) 2 (E = S, Se) with alkyl and acyl halides for the synthesis of unsymmetrical chalcogenides [31,32]. Some of these reactions are highly stereoselective, particularly those leading to vinylic chalcogenides.…”

Section: Introductionmentioning

confidence: 99%