Base Promoted Preparation of Alkenylsilanols from Allylsilanes

Akiyama, Toru; Imazeki, Shigeaki

doi:10.1246/cl.1997.1077

Cited by 17 publications

(7 citation statements)

References 10 publications

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“…silanols in this manner has been observed before, but the proposed mechanism requires DMSO,12 which is not consistent with our observation. Treatment of the crude mixture with TBAF gave pure 7 as expected 3,13 in near quantitative yield.…”

contrasting

confidence: 87%

Strategies for protodesilylation of C-2 trialkylsilyl terminal alkenes

Anderson

Flaherty

2000

J. Chem. Soc., Perkin Trans. 1

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contrasting

confidence: 87%

Strategies for protodesilylation of C-2 trialkylsilyl terminal alkenes

Anderson

Flaherty

2000

J. Chem. Soc., Perkin Trans. 1

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“…The reaction proceeded smoothly in the presence of TBAF and a palladium catalyst, which provided the desired (E)-alkene 17 in 81% yield with complete retention of the stereochemistry. Our attempt on the coupling reaction of unactivated 4aa under Anderson's conditions [48] and on exchanging the phenyl group of 4aa with a hydroxy group under Akiyama's conditions [49][50] resulted in the decomposition of the substrate. Next, we expanded the potential utility of these alkenylsilanes via epoxidation of the 2-silylated allylic alcohol 4da (Scheme 3B).…”

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.

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“…R f ϭ 0.37 (hexane/ EtOAc,92:8) (2 C), 133.93, 136.57, 145.23, 158.84, 169.87 (2 C) ppm. EI MS: m/z (%) ϭ 383 (0.4) [M ϩ 1] ϩ , 382 (1) [M] ϩ , 336 (1.5), 333 (2.5), 299 (2.5), 292 (3.5), 309 (2.5), 291 (19), 245 (5.5), 235 (11), 218 (9.5), 217 (100), 189 (12), 161 (6), 149 (14), 145 (26), 135 (27), 121 (20), 91 (51). C 23 H 26 O 5 (382.5): calcd.…”

Section: Ethyl 2-ethoxycarbonylmentioning

confidence: 99%

“…Recently, we have reported [9] a general method for the preparation of 1-substituted alkenyl(phenyl)silanes 1a and 1b from 2-silylalkylidene derivative 2 [10] (Scheme 1), and so we decided to convert these silanes into the corresponding silanols 3a and 3b. Scheme A PhMe 2 Si group in alkenylsilanes is known to be convertible into a Me 2 SiOH group by a nucleophilic attack on silicon by a strong base such as tBuOK/18-crown-6 in the presence [11] or absence [12] of DMSO. Unfortunately, these methods did not provide the desired silanols with silanes 1a and 1b.…”

Section: Preparation Of Alkenylsilanolsmentioning

confidence: 99%