- Metal-free hydrogen evolution cross-coupling enabled by synergistic photoredox and polarity reversal catalysis
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A synergistic combination of photoredox and polarity reversal catalysis enabled a hydrogen evolution cross-coupling of silanes with H2O, alcohols, phenols, and silanols, which afforded the corresponding silanols, monosilyl ethers, and disilyl ethers, respectively, in moderate to excellent yields. The dehydrogenative cross-coupling of Si-H and O-H proceeded smoothly with broad substrate scope and good functional group compatibility in the presence of only an organophotocatalyst 4-CzIPN and a thiol HAT catalyst, without the requirement of any metals, external oxidants and proton reductants, which is distinct from the previously reported photocatalytic hydrogen evolution cross-coupling reactions where a proton reduction cocatalyst such as a cobalt complex is generally required. Mechanistically, a silyl cation intermediate is generated to facilitate the cross-coupling reaction, which therefore represents an unprecedented approach for the generation of silyl cationviavisible-light photoredox catalysis.
- Cao, Jilei,Lu, Kanghui,Ma, Lishuang,Yang, Xiaona,Zhou, Rong
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supporting information
p. 8988 - 8994
(2021/11/23)
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- General Synthesis of Trialkyl-And Dialkylarylsilylboranes: Versatile Silicon Nucleophiles in Organic Synthesis
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Compared to carbon-based nucleophiles, the number of silicon-based nucleophiles that is currently available remains limited, which significantly hampers the structural diversity of synthetically accessible silicon-based molecules. Given the high synthetic
- Shishido, Ryosuke,Uesugi, Minami,Takahashi, Rikuro,Mita, Tsuyoshi,Ishiyama, Tatsuo,Kubota, Koji,Ito, Hajime
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supporting information
p. 14125 - 14133
(2020/09/16)
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- Palladium-Catalyzed Cross-Coupling of Silyl Electrophiles with Alkylzinc Halides: A Silyl-Negishi Reaction
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We report the first example of a silyl-Negishi reaction between secondary zinc organometallics and silicon electrophiles. This palladium-catalyzed process provides direct access to alkyl silanes. The delicate balance of steric and electronic parameters of the employed DrewPhos ligand is paramount to suppressing isomerization and promoting efficient and selective cross-coupling.
- Cinderella, Andrew P.,Vulovic, Bojan,Watson, Donald A.
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supporting information
p. 7741 - 7744
(2017/06/21)
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