Copper-Catalyzed Twofold Silylmetalation of Alkynes

Yamagishi, Hiroki; Shimokawa, Jun; Yorimitsu, Hideki

doi:10.1055/s-0037-1611869

Cited by 4 publications

(4 citation statements)

References 7 publications

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“…Upon treatment with PhB(pin), 3aa was converted to the corresponding oxaborole 8 in 85% yield, which overall addresses an entry to the rare anti -silylboration. , The reaction with Me 3 SiCl gave the 1,2-disilylated product 9 in 72% yield after quickly hydrolyzing the incipient O -silyl group of the crude material in methanol. The transformation represents a rare example of anti -disilylation of alkynes. , n Bu 3 SnCl and dimethyl disulfide also reacted with alkenyllithium 3aa to afford the corresponding alkenylstannane 10 (61%) and the alkenyl sulfide 11 (96%), respectively, as representative anti -silylstannylation and anti -silylsulfenylation. Alkylation of 3aa was also possible by using dimethyl sulfate as an electrophile to result in the formation of methylated product 12 in 90% yield.…”

Section: Resultsmentioning

confidence: 99%

“…The transformation represents a rare example of anti-disilylation of alkynes. 48,49 nBu 3 SnCl and dimethyl disulfide also reacted with alkenyllithium 3aa to afford the corresponding alkenylstannane 10 (61%) and the alkenyl sulfide 11 (96%), respectively, as representative anti-silylstannylation and anti-silylsulfenylation. Alkylation of 3aa was also possible by using dimethyl sulfate as an electrophile to result in the formation of methylated product 12 in 90% yield.…”

Section: ■ Introductionmentioning

confidence: 99%

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Regioselective Anti-Silyllithiation of Propargylic Alcohols

et al. 2022

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Among the known hydrosilylation or carbosilylation conditions of alkynes, anti-addition of the two units across the triple bond is considered rare compared to the syn counterpart. For anti-silylative vicinal difunctionalizations, transition-metal catalysts, such as ruthenium or palladium complexes, are generally required. Accordingly, silyl alkali metals have not been employed for those anti-addition transformations. Here we demonstrate that silyllithiums can add across the triple bond of a series of propargylic alkoxides regioselectively in an anti-fashion. Upon treatment with a variety of electrophiles, the trisubstituted alkenyl lithium intermediates were transformed into highly functionalized β-silyl allylic alcohols with high regiocontrol, eventually providing tri-or tetrasubstituted alkenylsilanes stereoselectively. A classic trick for anti-addition with propargylic alkoxides has transformed anti-silylative functionalizations into a robust and reliable strategy.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Regioselective Anti-Silyllithiation of Propargylic Alcohols

et al. 2022

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“…The transformation represents a rare example of anti-disilylation of alkynes. [44][45] nBu3SnCl and dimethyl disulfide also reacted with alkenyllithium 3aa to afford the corresponding alkenylstannane 10 (61%) and the alkenyl sulfide 11 (96%) respectively as representative anti-silylstannylation and antisilylsulfenylation. Alkylation of 3aa was also possible by using dimethyl sulfate as an electrophile to result in the formation of methylated product 12 in 90% yield.…”

Section: Resultsmentioning

confidence: 99%

Regioselective anti-Silyllithiation of Propargylic Alcohols

Karad

Saito

Shimokawa

et al. 2022

Preprint

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Among the known hydrosilylation or carbosilylation conditions of alkynes, anti-addition of the two units across the triple bond is considered rare compared to the syn counterpart. For anti-silylative vicinal difunctionalizations, transition-metal catalysts, such as ruthenium or palladium complexes, are generally required. Accordingly, silyl alkali metals have not been employed for those anti-addition transformations. Here we demonstrate that silyllithiums can add across the triple bond of a series of propargylic alkoxides regioselectively in an anti-fashion. Upon treatment with a variety of electrophiles, the tri-substituted alkenyl lithium intermediates were transformed into highly functionalized β-silyl allylic alcohols with high regio-control, eventually providing tri- or tetrasubstituted alkenylsilanes stereoselectively. A classic trick for anti-addition with propargylic alkoxides has transformed anti-silylative functionalizations into a robust and reliable strategy.

show abstract

“…The transformation represents a rare example of anti-disilylation of alkynes. [44][45] nBu3SnCl and dimethyl disulfide also reacted with alkenyllithium 3aa to afford the corresponding alkenylstannane 10 (61%) and the alkenyl sulfide 11 (96%) respectively as representative anti-silylstannylation and antisilylsulfenylation products. Alkylation of 3aa was also possible by using dimethyl sulfate as an electrophile to result in the formation of methylated product 12 in 90% yield.…”

Section: Resultsmentioning

confidence: 99%

Regioselective anti-Silyllithiation of Propargylic Alcohols

Karad

Saito

Shimokawa

et al. 2022

Preprint

Self Cite

View full text Add to dashboard Cite

Among the known hydrosilylation or carbosilylation conditions of alkynes, anti-addition of the two units across the triple bond is considered rare compared to the syn counterpart. For anti-silylative vicinal difunctionalizations, transition-metal catalysts, such as ruthenium or palladium complexes, are generally required. Accordingly, silyl alkali metals have not been employed for those anti-addition transformations. Here we demonstrate that silyllithiums can add across the triple bond of a series of propargylic alkoxides regioselectively in an anti-fashion. Upon treatment with a variety of electrophiles, the tri-substituted alkenyl lithium intermediates were transformed into highly functionalized β-silyl allylic alcohols with high regio-control, eventually providing tri- or tetrasubstituted alkenylsilanes stereoselectively. A classic trick for anti-addition with propargylic alkoxides has transformed anti-silylative functionalizations into a robust and reliable strategy.

show abstract

Copper-Catalyzed Twofold Silylmetalation of Alkynes

Cited by 4 publications

References 7 publications

Regioselective Anti-Silyllithiation of Propargylic Alcohols

Regioselective Anti-Silyllithiation of Propargylic Alcohols

Regioselective anti-Silyllithiation of Propargylic Alcohols

Regioselective anti-Silyllithiation of Propargylic Alcohols

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