Transition-metal-catalyzed enantioselective C−H silylation

Chem Catalysis, Год журнала: 2022, Номер 2(11), С. 2898 - 2928

Опубликована: Авг. 15, 2022

Язык: Английский

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Highly Enantioselective Construction of Multifunctional Silicon‐Stereogenic Silacycles by Asymmetric Enamine Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(9)

Опубликована: Янв. 10, 2023

We report the first highly enantioselective construction of silicon-stereocenters by asymmetric enamine catalysis. An unprecedented desymmetric intramolecular aldolization prochiral siladials was thus developed for facile access multifunctional silicon-stereogenic silacycles in high to excellent enantioselectivity. With an enal moiety, these adducts could be readily elaborated diverse synthesis compounds, and late-stage modification.

Язык: Английский

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Chiral Silanols: Strategies and Tactics for Their Synthesis

Chemistry - A European Journal, Год журнала: 2023, Номер 29(19)

Опубликована: Янв. 9, 2023

Silanols are valuable and important compounds, which have found widespread applications in the field of materials science, synthetic chemistry, medicinal chemistry. Although a handful approaches been developed for synthesis various silanols, access to enantioenriched silicon-stereogenic silanols remains underdeveloped. This Concept article intends summarize highlight recent advances construction endeavors encourage further research this area.

Язык: Английский

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Catalytic Kinetic Resolution of Monohydrosilanes via Rhodium‐Catalyzed Enantioselective Intramolecular Hydrosilylation

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(25)

Опубликована: Апрель 12, 2024

The catalytic access of silicon-stereogenic organosilanes remains a big challenge, and largely depends on the desymmetrization symmetric precursors with two identical substitutes attached to silicon atom. Here we report construction via kinetic resolution racemic monohydrosilanes good excellent selectivity factors. Both Si-stereogenic dihydrobenzosiloles could be efficiently accessed in one single operation Rh-catalyzed enantioselective intramolecular hydrosilylation, employing (R,R)-Et-DuPhos as optimal ligand. This protocol features mild conditions, low catalyst loading (0.1 mol % [Rh(cod)Cl]

Язык: Английский

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Organocatalytic enantioselective construction of Si-stereocenters: recent advances and perspectives

Chemical Society Reviews, Год журнала: 2024, Номер 53(17), С. 8546 - 8562

Опубликована: Янв. 1, 2024

Silicon-stereogenic chiral organosilanes have found increasing applications in synthetic chemistry, medicinal and materials science. In this context, various asymmetric catalytic methods been established for the diverse synthesis of silicon-stereogenic silanes. particular, organocatalysis is emerging as an important complementary tool enantioselective construction silicon-stereocenters, along with rapid development chiral-metal catalyzed protocols. Its advent provides a powerful platform to achieve functionalized structural diversity, should lead great organosilicon chemistry. Tutorial Review, we highlight these latest achievements from two aspects: desymmetrizations prochiral tetraorganosilanes dynamic kinetic transformations racemic by employing five organocatalytic activation modes. The advantages, limitations value each protocol, well opportunities still open further exploration, are also discussed.

Язык: Английский

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Catalytic Asymmetric Dehydrogenative Si–H/X–H Coupling toward Si-Stereogenic Silanes

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Янв. 22, 2025

ConspectusChiral organosilicon compounds bearing a Si-stereogenic center have attracted increasing attention in various scientific communities and appear to be topic of high current relevance modern organic chemistry, given their versatile utility as chiral building blocks, reagents, auxiliaries, catalysts. Historically, access these non-natural silanes mainly relies on resolution, whereas asymmetric synthetic methods dramatically lagged compared carbon counterparts. Over the past two decades, transition-metal-catalyzed desymmetrization prochiral organosilanes has emerged an effective tool for synthesis enantioenriched silanes. Despite progress, catalytic reactions usually suffer from limited substrate scope, poor functional-group tolerance, low enantioselectivity. The growing demand with structural diversity continued drive development new practical assembly molecules.Five years ago, our research group embarked project aimed at developing general approach that can unlock functionalized efficiency. This Account describes laboratory's endeavor exploration dehydrogenative Si–H/X–H coupling toward features (1) readily accessible dihydrosilane starting materials; (2) diverse X–H (X═C, N, O, etc.) partners; (3) platform transformable monohydrosilane products; (4) efficiency atomic economy.At initial stage research, biaryl was selected model conduct enantioselective intramolecular C–H/Si–H reaction. Rh/Josiphos system found early this process, while final enantiocontrol elusive. Mechanistic studies indicated rhodium silyl dihydride complex is resting state cycle, which may undergo racemization center. Enlightened by mechanistic investigations, strategies, tandem alkene hydrosilylation strategy bulky alkene-assisted strategy, were adopted avoid racemization, delivering corresponding 9-silafluorenes excellent yields enantioselectivities. Further C(sp2)–H or C(sp3)–H silylation gave series five-, six- seven-membered heterocycles Next, we extended reaction intermolecular version, realizing Si–H/C–H, Si–H/O–H, Si–H/N–H variety acyclic monohydrosilanes, ethers, siloxanes, silanols, silazanes. We also presented endeavors apply resulting compounds, including further derivatization, polymerization, chiroptical property successfully introduced Si-stereocenters into bioactive molecules, polymers, materials. Lastly, based understanding metal species, developed type ligand applied enable atroposelective anticipate methodology, insights, studies, will not only inspire chemistry but contribute creation novel molecules medicinal materials science.

Язык: Английский

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Enantioselective construction of Si-stereogenic linear alkenylhydrosilanes via copper-catalyzed hydrosilylation of alkynes

Chem Catalysis, Год журнала: 2024, Номер 4(2), С. 100887 - 100887

Опубликована: Янв. 15, 2024

Язык: Английский

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Construction of Si‐Stereogenic Silanols by Palladium‐Catalyzed Enantioselective C−H Alkenylation

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(20)

Опубликована: Фев. 27, 2024

The construction of silicon-stereogenic silanols via Pd-catalyzed intermolecular C-H alkenylation with the assistance a commercially available L-pyroglutamic acid has been realized for first time. Employing oxime ether as directing group, silanol derivatives could be readily prepared excellent enantioselectivities, featuring broad substrate scope and good functional group tolerance. Moreover, parallel kinetic resolution unsymmetric substrates further highlighted generality this protocol. Mechanistic studies indicate that stabilize Pd catalyst provide chiral induction. Preliminary computational unveil origin enantioselectivity in bond activation step.

Язык: Английский

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Cu(I)-Catalyzed Chemo- and Enantioselective Desymmetrizing C–O Bond Coupling of Acyl Radicals

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(11), С. 6535 - 6545

Опубликована: Март 13, 2023

Transition-metal-catalyzed enantioselective functionalization of acyl radicals has so far not been realized, probably due to their relatively high reactivity, which renders the chemo- and stereocontrol challenging. Herein, we describe Cu(I)-catalyzed desymmetrizing C-O bond coupling radicals. This reaction is compatible with (hetero)aryl alkyl aldehydes and, more importantly, displays a very broad scope challenging alcohol substrates, such as 2,2-disubstituted 1,3-diols, 2-substituted-2-chloro-1,3-diols, 2-substituted 1,2,3-triols, serinols, meso primary 1,4-diols, providing enantioenriched esters characterized by acyclic tetrasubstituted carbon stereocenters. Partnered one- or two-step follow-up transformations, this provides convenient practical strategy for rapid preparation chiral C3 building blocks from readily available alcohols, particularly industrially relevant glycerol. Mechanistic studies supported proposed

Язык: Английский

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Generation of Silicon-Centered Stereogenicity by Chiral Counteranion-Directed Desymmetrization of Silanediols

ACS Catalysis, Год журнала: 2023, Номер 13(15), С. 10244 - 10247

Опубликована: Июль 21, 2023

An enantiotopic group-selective monosilylation of silanediols using List's counteranion-directed silylation methodology is reported. A silylium-ion-like silicon electrophile generated from an allylic silane paired with imidodiphosphorimidate (IDPi) enables the enantioselective discrimination two hydroxy groups attached to prochiral atom. The enantioselectivity achieved in desymmetrization step further improved by a subsequent kinetic resolution arrive at silicon-stereogenic disiloxanes high enantiocontrol, along minor amounts achiral trisiloxane byproduct.

Язык: Английский

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