Copper Catalyzed Formation of Carbon–Silicon Bond: A Review

Journal of Inorganic and Organometallic Polymers and Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 1, 2025

Language: Английский

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Rational design of dimeric 1,3-diphenylisobenzosilole (DPBS) for better optoelectronic applications and their photophysical properties

Computational and Theoretical Chemistry, Journal Year: 2025, Volume and Issue: 1244, P. 115060 - 115060

Published: Jan. 5, 2025

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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Recent Advances in Catalytic Enantioselective Construction of Monofluoromethyl-Substituted Stereocenters

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(85), P. 12302 - 12314

Published: Jan. 1, 2024

Chiral organofluorine compounds featuring a monofluoromethyl (CH

Language: Английский

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Enantioselective construction of silicon-stereogenic vinylsilanes from simple alkenes

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 18, 2025

The diverse utility of acyclic vinylsilanes has driven the interest in synthesis enantioenriched bearing a Si-stereogenic center. However, predominant approaches for catalytic asymmetric generation have mainly relied on transition metal-catalyzed reactions alkynes with different silicon sources. Here we successfully realize enantioselective linear silicon-stereogenic good yields and enantiomeric ratios from simple alkenes under rhodium catalysis. significance this transformation lies its ability to achieve regioconvergent enantioconvergent conversion, efficiently transforming petroleum-derived isomeric mixtures olefin feedstocks into single regio- stereoisomer product. practicality method is further exemplified by downstream transformations these leveraging functionality leaving group nature aryl substituent as well development chiral π-conjugated double bond systems.

Language: Английский

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Synthesis of Inherently Chiral Germepins via Rh-Catalyzed Enantioselective C–H Germylation

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 15, 2025

A rhodium-catalyzed enantioselective C-H germylation reaction was developed, enabling the synthesis of germepin derivatives with diverse substitutions. This study represents a rare application E-H/C-H (E = Si or Ge) dehydrogenation coupling reactions in synthesizing inherently chiral molecules, marking first successful seven-membered heterocycles containing group 14 elements. Compared to their structurally analogous tribenzosilepins, tribenzogermepins exhibit enhanced stereochemical stability under conditions. Furthermore, compatibility Si-H bond identical conditions highlights distinct reactivity and Ge-H bonds.

Language: Английский

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Rhodium-catalyzed synthesis of Si-stereogenic alkoxysilanes and silyl enol ethers via hydrosilylation of carbonyl compounds

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(93), P. 13734 - 13737

Published: Jan. 1, 2024

An efficient catalytic asymmetric hydrosilylation of aldehydes, ketones, and α,β-unsaturated ketones toward Si-stereogenic alkoxysilanes silyl enol ethers is developed.

Language: Английский

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Enantioselective Synthesis of Nonfused Eight-Membered O-Heterocycles by Sequential Catalysis

Organic Letters, Journal Year: 2024, Volume and Issue: 27(1), P. 340 - 345

Published: Dec. 30, 2024

This work describes a chiral bifunctional squaramide/DBU sequential catalytic strategy for the enantioselective synthesis of nonfused eight-membered O-heterocycles through asymmetric addition ynones to β,γ-unsaturated α-ketoesters followed by regio- and diastereoselective cyclization adduct intermediates. Mechanistic experiments revealed that an isomerization process should be involved in ring formation step, origin high regioselectivity diastereoselectivity has also been elucidated DFT calculations.

Language: Английский

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Iodine Rearrangements of Tetraallylsilane and Synthesis of Silicon-Stereogenic Organosilanes

International Journal of Molecular Sciences, Journal Year: 2024, Volume and Issue: 25(18), P. 9996 - 9996

Published: Sept. 17, 2024

Tetraallylsilane can undergo either a mono or double rearrangement when treated with iodine (I2). The extent of depends on the equivalents I2 used, where 1 equivalent gives high yields mono-rearranged products and excess (e.g., 3 equivalents) causes to occur. This transformation be applied synthesis potentially valuable silicon-stereogenic organosilanes.

Language: Английский

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Enantioselective Synthesis of Axially Chiral Silacyclohexylidene Oxime Ethers by Chiral Phosphoric Acid Catalysis

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 17, 2024

Abstract The first asymmetric condensation of prochiral silacyclohexanones with hydroxylamines by chiral phosphoric acid catalysis has been developed, which provides a facile and straightforward protocol for the enantioselective construction valuable axially silacyclohexylidene oxime ethers that are otherwise inaccessible. Notably, this constitutes rare example accessing silacycles featuring axial chirality.

Language: Английский

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