- NEW (TRIORGANOSILYL)ALKYNES AND THEIR DERIVATIVES AND A NEW CATALYTIC METHOD FOR OBTAINING NEW AND CONVENTIONAL SUBSTITUTED (TRIORGANOSILYL)ALKYNES AND THEIR DERIVATIVES
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The present invention relates to new (triorganosilyl)alkynes and their derivatives having general formula 1 R1—C≡C—Z (I) In its second aspect, this invention relates to a new selective method for the preparation of new and conventional (triorga
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Paragraph 0110; 0133 - 0139
(2014/02/15)
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- NEW (TRIORGANOSILYL)ALKYNES AND THEIR DERIVATIVES AND A NEW CATALYTIC METHOD FOR OBTAINING NEW AND CONVENTIONAL SUBSTITUTED (TRIORGANOSILYL)ALKYNES AND THEIR DERIVATIVES
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The present invention relates to new (triorganosilyl)alkynes and their derivatives having general formula 1 R1-C≡C-Z (I) In its second aspect, this invention relates to a new selective method for the preparation of new and conventional (triorga
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Page/Page column 12-13
(2012/07/14)
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- Silylative coupling of terminal alkynes with iodosilanes: New catalytic activation of sp-hybridized carbon-hydrogen bonds
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The [{Ir(μ-Cl)(CO)2}2] (I)-catalyzed reaction of terminal alkynes and diynes with Me3SiI with the aid of NEt(i-Pr)2 occurs smoothly, leading to the formation of mono- and bis-silyl-functionalized alkynyl derivat
- Kownacki, Ireneusz,Marciniec, Bogdan,Dudziec, Beata,Kubicki, MacIej
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experimental part
p. 2539 - 2545
(2011/06/27)
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- The intricate assembling of gem-diphenylpropargylic units
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While optimized procedures for selective propargylic - versus allenic - attack (in particular by alkynylsilanes) have proven to be compatible with many substitution patterns at the propargylic center, the case of diarylpropargyl electrophiles has remained problematic. The intrinsic reactivity of 1,1-diphenylpropargylic alcohols [R-C≡C-C(Ph2)OH (R = TMS, H, Me)] in the presence of various acids (and in the absence of additional nucleophile) has thus been systematically investigated. Whereas the monophenyl analogues [R-C≡C-CH(Ph)OH] afford the expected bis(phenylpropargyl) ethers, the diphenyl versions undergo complex but quite selective processes to afford various structural types: depending on the acid used, a diallene, an allenyne, an indenylallene, an indanone or a condensed tetra- and pentacycles were obtained. When the reactions were conducted in the presence of an alkynylsilane capable of playing the role of a competing nucleophile, the expected propargylic substitution products - dialkynyldiphenylmethanes or their isomers - were never observed. The hitherto unknown simple hydrocarbons diethynyl- and dipropynyl-diphenylmethane could, however, be obtained in low yields through a four-step sequence involving allenylidene- and alkynylruthenium intermediates. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Maraval, Valerie,Duhayon, Carine,Coppel, Yannick,Chauvin, Remi
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experimental part
p. 5144 - 5156
(2009/08/07)
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- Novel carbon-carbon bond-forming reactions using carbocations produced from substituted propargyl silyl ethers by the action of TMSOTf
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Highly useful carbon-carbon bond forming reactions using stable allenyl, propargyl, or allyl-propargyl hybrid cations have been developed. These carbocations could be generated from silyl 1-(π-donor)-substituted propargyl ethers by the action of trimethylsilyl trifluoromethanesulfonate in dichloromethane at -78 °C to room temperature and could be attacked nucleophilically by electron rich arenes, allylsilanes, or enol silyl ethers, giving rise to allenes, alkynes, and their derivatives. A novel method for regio- and stereoselective synthesis of conjugated enynes utilizing allyl-propargyl hybrid cations has also been established.
- Ishikawa,Okano,Aikawa,Saito
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p. 4635 - 4642
(2007/10/03)
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