Catalytic Asymmetric Dehydrogenative Si–H/N–H Coupling: Synthesis of Silicon-Stereogenic Silazanes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(21), P. 11727 - 11734

Published: May 19, 2023

Despite growing progress in the construction of silazanes, catalytic asymmetric synthesis silicon-stereogenic silazanes is significantly less explored and remains a considerable challenge. Herein, we report highly enantioselective via dehydrogenative coupling dihydrosilanes with anilines. The reaction readily produces wide range chiral bis-silazanes excellent yields stereoselectivities (up to 99% ee). Further utility this process demonstrated by polycarbosilazanes featuring configurational main chain chirality. In addition, straightforward transformation enantioenriched delivers various silane compounds stereospecific fashion, illustrating their potential utilities as synthons for novel silicon-containing functional molecules.

Language: Английский

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X-type silyl ligands for transition-metal catalysis

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4648 - 4673

Published: Jan. 1, 2024

This review summarizes the developments of X-type silyl ligands for transition-metal catalysis, elucidating unique features σ-donating ability and trans -influence silyl–metal catalysts.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(25)

Published: April 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]

Language: Английский

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The role of silicon in drug discovery: a review

RSC Medicinal Chemistry, Journal Year: 2024, Volume and Issue: 15(10), P. 3286 - 3344

Published: Jan. 1, 2024

This review aims to highlight the role of silicon in drug discovery.

Language: Английский

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

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(17), P. 8546 - 8562

Published: Jan. 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.

Language: Английский

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Copper‐Catalyzed Asymmetric Synthesis of Silicon‐Stereogenic Benzoxasiloles

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(7)

Published: Jan. 5, 2024

Abstract A Cu‐catalyzed asymmetric synthesis of silicon‐stereogenic benzoxasiloles has been realized via intramolecular Si−O coupling [2‐(hydroxymethyl)phenyl]silanes. Cu(I)/difluorphos is found to be an efficient catalytic system for enantioselective Si−C bond cleavage and formation. In addition, kinetic resolution racemic substituted [2‐(hydroxymethyl)phenyl]silanes using Cu(I)/ PyrOx (pyridine‐oxazoline ligands) as the developed afford carbon‐ benzoxasiloles. Ring‐opening reactions chiral with organolithiums Grignard reagents yield various enantioenriched functionalized tetraorganosilanes.

Language: Английский

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Catalytic Asymmetric Construction of C‐ and Si‐Stereogenic Silacyclopentanes via Hydrosilylation of Arylmethylenecyclopropanes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(48)

Published: Aug. 14, 2024

Silacycles have exhibited significant potential for application in the fields of medicinal chemistry, agrochemistry, and materials science. Accordingly, development effective methods synthesizing these compounds has attracted increasing attention. Here, we report an efficient Cu-catalyzed enantioselective hydrosilylation arylmethylenecyclopropanes with hydrosilanes, that allows rapid assembly various enantioenriched carbon- silicon-stereogenic silacyclopentanes good yields excellent enantioselectivities diastereoselectivities under mild conditions. Further stereospecific transformation Si-H bond on chiral silicon center expands diversity C- Si-stereogenic silacyclopentanes.

Language: Английский

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

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: Feb. 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.

Language: Английский

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Enantioconvergent construction of stereogenic silicon via Lewis base-catalyzed dynamic kinetic silyletherification of racemic chlorosilanes

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Aug. 14, 2023

Organosilanes possessing an enantioenriched stereogenic silicon center are important in many branches of chemistry, yet they remain challenging to synthesize a practical and scalable way. Here we report dynamic kinetic silyletherification process racemic chlorosilanes with (S)-lactates using 4-aminopyridine as Lewis base catalyst. This enantioconvergent approach asymmetrically constructs the different manner from traditional resolution or desymmetrization. A range silylethers have been prepared high diastereoselectivity on up 10 g-scale, allowing synthesis diverse organosilane analogs.

Language: Английский

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