Copper Catalyzed Formation of Carbon–Silicon Bond: A Review

Journal of Inorganic and Organometallic Polymers and Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 1, 2025

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 silicon-stereogenic vinylsilanes from simple alkenes

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 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.

Язык: Английский

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Enantioselective Synthesis of Silicon-Stereogenic Siladihydrofuran Via Copper-Catalyzed Si-C Bond Cleavage

Опубликована: Янв. 1, 2025

Язык: Английский

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Enantioselective synthesis of silicon-stereogenic siladihydrofuran via copper-catalyzed Si-C bond cleavage

Journal of Catalysis, Год журнала: 2025, Номер unknown, С. 116089 - 116089

Опубликована: Март 1, 2025

Язык: Английский

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Silylative Kinetic Resolution of Acyclic Secondary Benzylic Alcohols Catalyzed by Chiral Guanidine Having Axial Chirality Containing a Methoxy Group

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 23, 2025

Comprehensive Summary New chiral guanidine catalysts having axial chirality containing a methoxy group were synthesized. Subsequently, their catalytic ability was examined by applying the silylative kinetic resolution of racemic alcohols using chlorosilanes. Based on an X‐ray crystallographic analysis catalysts, functional role predicted, and plausible reaction pathways transition state described. It also revealed that existence hydrogen bonding between catalyst atom at C‐1 position substrates great importance for attaining high selectivity reactivity. The proposed method is applicable to various acyclic aryl, heteroaryl, normal‐alkyl exhibiting medium s ‐values ( = 15–96, 15 examples).

Язык: Английский

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Isothiourea Catalysed Enantioselective Generation of Point and Axially Chiral Iminothia- and Iminoselenazinanones

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Symmetrical and unsymmetrical thioureas, as well selenoureas, are used in an isothiourea-catalysed Michael addition-lactamisation protocol using α,β-unsaturated pentafluorophenyl esters to generate iminothia- iminoselenazinanone heterocycles with high enantioselectivity (up 99 : 1 er). The scope limitations of this process have been widely investigated (40 examples total) thio- selenoureas containing ortho-substituted N-aryl substituents giving atropisomeric products, leading effective for iminoselenazinanones heterocyclic products both point axially chiral stereogenic elements excellent stereocontrol >95 5 dr 98 2 Mechanistic investigation showed that (i) the catalytically liberated aryloxide could deprotonate electron-deficient thiourea; (ii) absence isothiourea catalyst, leads formation racemic product; (iii) a crossover experiment indicates reversibility thia-Michael addition. Computational analysis has identified factors within process, arising from lactamisation step catalytic cycle.

Язык: Английский

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Synthesis of chiral germanium center enabled by poly-deborylative alkylation and desymmetrization

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Май 30, 2025

Chiral germanium centers are historically undervalued due to their extremely limited synthetic accessibility. Although shares similar chemical properties with silicon, synthesizing chiral proves significantly more challenging. To facilitate rapid access centers, we develop two strategies: deborylative alkylation of chlorides and copper-catalyzed diol desymmetrization. The α-boryl carbanion is demonstrated be an exceptional coupling partner for chloride, yielding 1,3-prochiral diols, which subsequently undergo desymmetrization afford centers. By combining these methodologies, successfully transform simple tetrachloride into a center in merely four steps, representing significant advancement main-group element chirality. Additionally, this strategy efficiently facilitates the construction silicon-stereogenic as well. Subsequent deoxygenative cross-coupling reactions products further expand scope organogermanium chemistry, revealing entirely new possibilities.

Язык: Английский

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Palladium-catalyzed double activation of Si-C(sp3) bond of benzosilacyclobutenes synergized with unexpected olefin migration and ring-opening hydrolysis

Journal of Catalysis, Год журнала: 2024, Номер 440, С. 115788 - 115788

Опубликована: Окт. 10, 2024

Язык: Английский

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

Chemical Communications, Год журнала: 2024, Номер 60(93), С. 13734 - 13737

Опубликована: Янв. 1, 2024

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

Язык: Английский

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