Cobalt-Catalyzed Sequential Site- and Stereoselective Hydrosilylation of 1,3- and 1,4-Enynes

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(12), P. 5233 - 5240

Published: March 17, 2022

Catalytic sequential hydrosilylation of 1,3-enynes and 1,4-enynes promoted by cobalt complexes derived from bisphosphines are presented. Site- stereoselective Si–H addition primary silanes to followed intramolecular diastereo- enantioselective afforded enantioenriched cyclic alkenylsilanes with simultaneous construction a carbon-stereogenic center silicon-stereogenic center. Reactions proceeded through isomerization the alkene moiety site- hydrosilylation. A wide range were in high efficiency selectivity. Functionalization containing stereogenic at silicon delivered variety chiral building blocks that otherwise difficult access.

Language: Английский

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P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(14), P. 8657 - 8739

Published: July 2, 2024

Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality and P-stereogenic ligands. Most reported belong to former class. Privileged ones such as BINAP DuPhos frequently employed wide range catalytic transformations. In contrast, latter class has remained small family many years mainly because their synthetic difficulty. The late 1990s saw emergence novel with superior enantioinduction ability Rh-catalyzed hydrogenation reactions. Since then, numerous have been synthesized used This Review summarizes thus far, including stereochemical electronic properties that afford high excellent enantioselectivities. Examples reactions use this described together applications construction key intermediates natural products therapeutic agents. literature covered dates back 1968 up until December 2023, centering on studies published later years.

Language: Английский

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Enantioselective Intermolecular C−H Silylation of Heteroarenes for the Synthesis of Acyclic Si‐Stereogenic Silanes

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(21)

Published: March 8, 2022

Intermolecular C-H silylation for the synthesis of acyclic silanes bearing a silicon-stereogenic center in one enantiomeric form remains unknown to date. Herein, we report first enantioselective intermolecular heteroarenes heteroarylsilanes. This process undergoes rhodium-catalyzed direct dehydrogenative Si-H/C-H cross-coupling, giving access variety heteroarylated monohydrosilanes, including bis-Si-stereogenic silanes, decent yields with excellent chemo-, regio-, and stereo-control, which significantly enlarge chemical space optically active monohydrosilanes.

Language: Английский

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Transition-metal-catalyzed enantioselective C−H silylation

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(11), P. 2898 - 2928

Published: Aug. 15, 2022

Language: Английский

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Cobalt‐Catalyzed Regio‐, Diastereo‐ and Enantioselective Intermolecular Hydrosilylation of 1,3‐Dienes with Prochiral Silanes

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(30)

Published: May 24, 2022

Abstract One of the most straightforward approaches to access chiral silanes is catalytic enantioselective hydrosilylation. Although significant advances have been achieved in construction either a carbon‐stereogenic center or silicon‐stereogenic through hydrosilylation, simultaneous establishment carbon‐ and an acyclic molecule single intermolecular hydrosilylation remained undeveloped. Herein, unprecedented cobalt‐catalyzed regio‐, diastereo‐ 1,3‐dienes presented, enabling transformation. A wide range bearing were generated high efficiency stereoselectivity. Functionalization enantioenriched delivered variety valuable building blocks that are otherwise difficult access.

Language: Английский

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Silicon‐Stereogenic Monohydrosilane: Synthesis and Applications

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: May 20, 2022

Abstract 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 architectures, monohydrosilanes, which bear a Si−H bond, hold unique position because of their facile transformations through stereospecific Si–carbon or Si–heteroatom bond‐formation reactions. In addition, those compounds also leveraged as for alcohol resolution, auxiliaries, mechanistic probes, well potential optoelectronic materials. This Minireview comprehensively summarizes synthesis applications silicon‐stereogenic particularly advances transition‐metal‐catalyzed asymmetric this class functional molecules.

Language: Английский

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Synthesis of Si‐Stereogenic Silanols by Catalytic Asymmetric Hydrolytic Oxidation

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: May 26, 2022

Despite growing progress in the construction of chiral organosilicon compounds, catalytic asymmetric synthesis silicon-stereogenic silanols is less explored and remains a considerable challenge. Herein, we report first enantioselective by hydrolytic oxidation dihydrosilanes. This practical procedure features ambient reaction conditions, high atom economy, good functional-group compatibility, H2 as only by-product, produces wide range valuable bis-silanols decent yields with excellent chemo- stereoselectivity.

Language: Английский

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Copper-Catalyzed Desymmetrization of Prochiral Silanediols to Silicon-Stereogenic Silanols

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(14), P. 8476 - 8483

Published: July 1, 2022

Despite the growing demand for enantioenriched silicon-stereogenic silanols in materials science, medicinal chemistry, and modern synthetic catalytic asymmetric synthesis of which remains a considerable challenge compared with their carbinol analogues. Herein, copper-catalyzed desymmetrization silanediols various functionalized chiral is demonstrated. The reaction features high atom economy, decent yield excellent stereoselectivity, H2 as sole byproduct. Key to success discrimination gem-diol groups silanediol relies on an enantioselective σ-bond metathesis process. Further straightforward elaboration delivers several interesting silane scaffolds without loss enantiopurities.

Language: Английский

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Rhodium‐Catalyzed Dynamic Kinetic Asymmetric Hydrosilylation to Access Silicon‐Stereogenic Center

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(51)

Published: Nov. 4, 2022

Abstract Strategies on the construction of enantiomerically pure silicon‐stereogenic silanes generally relies desymmetrization prochiral and symmetric substrates. However, dynamic kinetic asymmetric transformations organosilicon compounds have remained underdeveloped unforeseen owing to a lack an effective method for deracemization static silicon stereocenters. Here we report first Rh‐catalyzed intramolecular hydrosilylation (DyKAH) with “silicon‐centered” racemic hydrosilanes that enables facile preparation benzosiloles in good yields excellent enantioselectivities. The special rhodium catalyst controlled by non‐diastereopure‐type mixed phosphine‐phosphoramidite ligand axial chirality multiple stereocenters can induce enantioselectivity efficiently this novel DyKAH reaction. Density functional theory (DFT) calculations suggest amide moiety chiral plays important role facilitating S N 2 substitution chloride ion realize inversion center.

Language: Английский

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Catalytic asymmetric silicon-carbon bond-forming transformations based on Si-H functionalization

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(6), P. 1654 - 1687

Published: May 4, 2023

Language: Английский

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