Nickel-Catalyzed Hydrosilylation of Terminal Alkenes with Primary Silanes via Electrophilic Silicon–Hydrogen Bond Activation

Wu, Xiaoyu; Ding, Guo-Hui; Lu, Wenkui; Yang, Liqun; Wang, Jingyang; Zhang, Yuxuan; Xie, Xiaomin; Zhang, Zhaoguo

doi:10.1021/acs.orglett.1c00111

Cited by 26 publications

(22 citation statements)

References 69 publications

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“…Deuterosilanes are traditionally generated by the reaction of hazardous NaBD 4 or LiAlD 4 with corresponding chlorosilane, generating stoichiometric quantities of waste metal salts. 23 With increasing demand for deuterium-labeled products, catalysis provides a promising solution because of its inherently improved selectivity, functional group tolerance, and reduced waste. 24 − 26 Therefore, finding catalysts that facilitate the hydrogen/deuterium (H/D) exchange of hydrosilanes is desirable.…”

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confidence: 99%

Iron-Catalyzed H/D Exchange of Primary Silanes, Secondary Silanes, and Tertiary Siloxanes

et al. 2022

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A synthetic study into the catalytic hydrogen/deuterium (H/D) exchange of 1° silanes, 2° silanes, and 3° siloxanes is presented, facilitated by iron-β-diketiminato complexes ( 1a and 1b ). Near-complete H/D exchange is observed for a variety of aryl- and alkyl-containing hydrosilanes and hydrosiloxanes. The reaction tolerates alternative hydride source pinacolborane (HBpin), with quantitative H/D exchange. A synthetic and density functional theory (DFT) investigation suggests that a monomeric iron-deuteride is responsible for the H/D exchange.

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confidence: 99%

Iron-Catalyzed H/D Exchange of Primary Silanes, Secondary Silanes, and Tertiary Siloxanes

et al. 2022

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“…The catalytic mechanism of hydrosilylation of alkenes is generally considered as the Chalk–Harrod mechanism or modified Chalk–Harrod mechanism. , In recent years, the mechanism of hydrosilylation of alkenes has been extensively studied. − Our group has also made progress in the study of the mechanism of cobalt-catalyzed hydrosilation of alkenes . In comparison with our reported [PSiP] pincer cobalt(I) complex, complex 1 has higher catalytic activity and better selectivity.…”

Section: Results and Discussionmentioning

confidence: 81%

[P, C] Chelate Cobalt(I)-Catalyzed Distinct Selective Hydrosilylation of Alkenes under Mild Conditions

et al. 2022

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The industrialization of alkene hydrosilylation catalyzed by cheap metals has become a research hotspot in recent years. Recently, we have found that [P, C] chelate cobalt(III) hydrides are active catalysts in the hydrosilylation of alkenes, but in this catalytic system, the real catalyst is [HCo(PMe3)3], and the [P, C] chelate ligand was not involved in the catalytic reaction. In this paper, to study the effect of the [P, C] chelate ligand on the hydrosilylation of alkenes, a [P, C] chelate cobalt(I) complex, [(Me3P)3Co(o-Ph2P-C6H4-CO)] (1), was prepared and used as a catalyst for the hydrosilylation of alkenes. To our surprise, it was found that complex 1 as a catalyst exhibits more efficient performance for the selective hydrosilylation of alkenes compared with the related [P, C] chelate cobalt(III) hydride, and the selectivity for aromatic alkenes is 100% Markovnikov but the selectivity for aliphatic alkenes is almost 100% anti-Markovnikov. The catalytic conditions (2.5 h, 30 °C) are very mild. For this catalytic system, the reaction activity of aliphatic alkenes is greater than that of aromatic alkenes. In the study of the catalytic mechanism, the intermediate with a coordinated η2-(Si–H) bond is considered as a real catalyst. The catalytic mechanism is proposed on the basis of experimental information and literature reports.

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“…3b ). Double bonds on skipped diene 3d could be selectively converted via hydrosilylation reaction to deliver 4-vinyl silane compound 7 51 . The 3d could aslo proceed alkylation-peroxidation with 1,3-dicarbonyl compounds and tert -butyl hydroperoxide to deliver functionalized carbonyl compound 8 (Fig.…”

Section: Resultsmentioning

confidence: 99%

Cobalt-catalyzed branched selective hydroallylation of terminal alkynes

Chen

Ying

2022

Nat Commun

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Here, we reported a cobalt-hydride-catalyzed Markovnikov-type hydroallylation of terminal alkynes with allylic electrophile to access valuable and branched skipped dienes (1,4-dienes) with good regioselectivity. This operationally simple protocol exhibits excellent functional group tolerance and exceptional substrate scope. The reactions could be carried out in gram-scale with TON (turn over number) up to 1160, and the products could be easily derivatized. The preliminary mechanism of electrophilic allylation of α-selective cobalt alkenyl intermediate was proposed based on deuterium labeling experiment and kinetic studies.

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Nickel-Catalyzed Hydrosilylation of Terminal Alkenes with Primary Silanes via Electrophilic Silicon–Hydrogen Bond Activation

Cited by 26 publications

References 69 publications

Iron-Catalyzed H/D Exchange of Primary Silanes, Secondary Silanes, and Tertiary Siloxanes

Iron-Catalyzed H/D Exchange of Primary Silanes, Secondary Silanes, and Tertiary Siloxanes

[P, C] Chelate Cobalt(I)-Catalyzed Distinct Selective Hydrosilylation of Alkenes under Mild Conditions

Cobalt-catalyzed branched selective hydroallylation of terminal alkynes

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