94286-52-9Relevant academic research and scientific papers
Palladium-Catalyzed Benzylic Silylation of Diarylmethyl Carbonates with Silylboranes under Base-Free Conditions
Asai, Kento,Hirano, Koji,Miura, Masahiro
supporting information, (2022/02/19)
A palladium-catalyzed benzylic silylation of diarylmethyl carbonates with silylboranes has been developed. The reaction proceeds smoothly even under external base-free conditions, and the corresponding benzylic silanes are formed in good to high yields. The obtained benzyl silane derivatives can work as the benzylic nucleophiles by the action of a suitable fluoride source and react with some carbon electrophiles to deliver the corresponding benzylic C?C cross-coupled products. Additionally, while still preliminary, the allylic silylation of the isoelectronic allylic carbonates is also achieved.
Regioselective Access to α-Vinylsilanes and α-Vinylgermanes by Cobalt-Catalyzed Migratory Hydrofunctionalization of 2-Alkynes
Chang, Sukbok,Kim, Dongwook,Park, Jung-Woo,Sahoo, Manoj Kumar
, p. 12777 - 12784 (2021/10/29)
While migratory functionalization of alkynes has been recognized as a unique way to access allylic functionalities via π-allyl metal intermediates, hydrofunctionalization of 2-alkynes to afford α-functional olefins has been unexplored. We describe herein the use of a cobalt hydride based system for regioselective migratory hydrofunctionalization of 2-alkynes to furnish α-vinylsilanes and α-vinylgermanes by a mechanistic understanding of the cobalt hydride species on alkyne π-bond migration. The key mechanism of alkyne π-bond migration by [bis(dicyclohexylphosphino)ethane]cobalt hydride is strongly supported by both experimental and computational studies, and the role of each reaction component, such as alkynes and silanes, is elucidated to rationalize the unique α-vinyl selectivity.
Silicon Grignard Reagents as Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution
Xue, Weichao,Oestreich, Martin
, p. 233 - 239 (2019/01/04)
A broad range of transition-metal catalysts is shown to promote allylic substitution reactions of allylic electrophiles with silicon Grignard reagents. The procedure was further elaborated for CuI as catalyst. The regioselectively is independent of the leaving group for primary allylic precursors, favoring α over γ. The stereochemical course of this allylic transposition was probed with a cyclic system, and anti -dia-stereoselectivity was obtained.
Silylative cyclopropanation of allyl phosphates with silylboronates
Shintani, Ryo,Fujie, Ryuhei,Takeda, Momotaro,Nozaki, Kyoko
, p. 6546 - 6549 (2014/06/24)
A potassium-bis(trimethylsilyl)amide-mediated cyclopropanation of allyl phosphates with silylboronates has been developed. Unlike the reported copper-catalyzed allylic substitution reactions, the nucleophile selectively attacks at the β-position of the allylic substrates under the present reaction conditions. The mechanism of this process has also been investigated, thus indicating the involvement of a silylpotassium species as the active nucleophilic component.
Copper-catalyzed Si-B bond activation in branched-selective allylic substitution of linear allylic chlorides
Vyas, Devendra J.,Oestreich, Martin
supporting information; experimental part, p. 8513 - 8515 (2011/01/05)
The harder they come, the better they leave! Chloride is superior to all common leaving groups in the γ-selective allylic substitution of linear precursors. This approach involves a novel copper-catalyzed Si-B bond activation (see scheme; γ/α≥98:2, 7-examples; Si=SiMe2Ph and B=Bpin with pin=pinacolato).
Expedient access to branched allylic silanes by copper-catalysed allylic substitution of linear allylic halides
Vyas, Devendra J.,Oestreich, Martin
supporting information; experimental part, p. 568 - 570 (2010/05/01)
An unprecedented copper-catalysed allylic transposition enables the regioselective synthesis of branched allylic silanes from linear allylic halides through direct C-Si bond formation.
A Synthesis of Allylsilanes in which the Silyl Group is at the More-substituted End of the Allyl Group
Fleming, Ian,Waterson, David
, p. 1809 - 1813 (2007/10/02)
The allylsilanes (8), (11), (18) - (20), and (26), have been made by a three-step sequence from αβ-unsaturated esters.The steps are conjugate addition of the phenyldimethylsilyl group, lithium aluminium hydride reduction, and selenium-mediated dehydration
