Catalytic Synthesis of Functional Silicon‐Stereogenic Silanes through <i>Candida antarctica</i> Lipase B Catalyzed Remote Desymmetrization of Silicon‐Centered Diols

Lü, Xing; Li, Li; Yang, Wei; Jiang, Kezhi; Yang, Ke‐Fang; Zheng, Zhan‐Jiang; Xu, Li‐Wen

doi:10.1002/ejoc.201300932

Cited by 32 publications

(6 citation statements)

References 85 publications

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“…[64] Transition-metal-catalyzed dehydrogenative SiÀ X (X = O, N, F, Cl, S) bond formation is also stereospecific, and could be used for the efficient construction of enantioenriched siloxanes and silyl halides. The Sommer group showcased that the Pdor Ni-catalyzed coupling of chiral monohydrosilane Si-1 with water, alcohol, and acid could afford the chiral silanol (55), alkoxy-or aryloxy-silane (56 or 57), and silyl ester (58) with inversion of configuration in a high stereospecific manner (79-99 % inversion; Scheme 37). [65] The use of Raney Ni resulted in higher efficiency and better stereospecificity than using Pd/C.…”

Section: Methodsmentioning

confidence: 99%

Silicon‐Stereogenic Monohydrosilane: Synthesis and Applications

Wang

2022

Angew Chem Int Ed

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Optically active organosilanes have been demonstrated to be versatile chiral reagents in synthetic chemistry since the early seminal contributions by Sommer and Corriu. Among these silicon‐containing chiral architectures, monohydrosilanes, which bear a Si−H bond, hold a unique position because of their facile transformations through stereospecific Si–carbon or Si–heteroatom bond‐formation reactions. In addition, those compounds have also been leveraged as chiral reagents for alcohol resolution, chiral auxiliaries, mechanistic probes, as well as potential optoelectronic materials. This Minireview comprehensively summarizes the synthesis and synthetic applications of silicon‐stereogenic monohydrosilanes, particularly the advances in the transition‐metal‐catalyzed asymmetric synthesis of this class of functional molecules.

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Section: Methodsmentioning

confidence: 99%

Silicon‐Stereogenic Monohydrosilane: Synthesis and Applications

Wang

2022

Angew Chem Int Ed

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“…Xu and coworkers reported an example of an enzyme-catalyzed remote desymmetrization of silicon-centered diols in 2013 (Scheme 31). [58] With Candida antarctica lipase B (CAL-B, Novozym 435) as the catalyst, the Si-containing diol 44 was enantioselectively protected by an acyl group when using ethanoic anhydride as the acylating reagent, thereby providing the enantioenriched silicon-stereogenic tetrasubstituted silanes with up to 78 % ee. Two examples of silicon-stereo-genic monohydrosilanes were also presented.…”

Section: Other Methodsmentioning

confidence: 99%

Silicon‐Stereogenic Monohydrosilane: Synthesis and Applications

Wang

2022

Angewandte Chemie

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Optically active organosilanes have been demonstrated to be versatile chiral reagents in synthetic chemistry since the early seminal contributions by Sommer and Corriu. Among these silicon-containing chiral architectures, monohydrosilanes, which bear a SiÀ H bond, hold a unique position because of their facile transformations through stereospecific Si-carbon or Si-heteroatom bond-formation reactions. In addition, those compounds have also been leveraged as chiral reagents for alcohol resolution, chiral auxiliaries, mechanistic probes, as well as potential optoelectronic materials. This Minireview comprehensively summarizes the synthesis and synthetic applications of silicon-stereogenic monohydrosilanes, particularly the advances in the transition-metal-catalyzed asymmetric synthesis of this class of functional molecules.

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“…Representative examples include the alcoholysis, hydrosilylation, − carbene insertion, , and dehydrogenative coupling − of dihydrosilanes; the ring expansion of silacyclobutanes; − the C–H functionalization of diarylsilanes; − the hydroboration of siladienes; and the [2 + 2 + 2] cycloaddition of silatriynes. , Despite these advances, to the best of our knowledge, the equally important, or even more so, environmentally benign metal-free organocatalyzed asymmetric approaches to the creation of silicon-stereogenic organosilicon compounds remain unexplored, probably owing to the lack of competent catalysts and substrates (Scheme ). , …”

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confidence: 99%

Stereoselective Access to Silicon-Stereogenic Silacycles via the Carbene-Catalyzed Desymmetric Benzoin Reaction of Siladials

Líu

Liao

et al. 2022

ACS Catal.

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The catalytic asymmetric synthesis of silicon-stereogenic organosilicon compounds has been a long-standing challenging task and was recently accomplished through a handful of transition-metal-catalyzed approaches. Herein we report an organocatalytic desymmetrization strategy for constructing optically active silicon-stereogenic silacycles. In the presence of a chiral N-heterocyclic carbene (NHC) catalyst, two identical formyl groups on the tetrasubstituted silanes are successfully discriminated to undergo stereoselective intramolecular benzoin reactions, affording enantioenriched dibenzo[b,f]silepin-10-ones featuring carbon- and silicon-stereogenic centers at the 1,4-positions, respectively. This catalytic process can be readily expanded to the gram scale, and the products can be further converted to other valuable molecules. DFT calculations were also conducted to unveil the reaction mechanism and the origins of the stereoselectivities.

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Catalytic Synthesis of Functional Silicon‐Stereogenic Silanes through Candida antarctica Lipase B Catalyzed Remote Desymmetrization of Silicon‐Centered Diols

Cited by 32 publications

References 85 publications

Silicon‐Stereogenic Monohydrosilane: Synthesis and Applications

Silicon‐Stereogenic Monohydrosilane: Synthesis and Applications

Silicon‐Stereogenic Monohydrosilane: Synthesis and Applications

Stereoselective Access to Silicon-Stereogenic Silacycles via the Carbene-Catalyzed Desymmetric Benzoin Reaction of Siladials

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