Synfacts, Год журнала: 2024, Номер 20(11), С. 1201 - 1201
Опубликована: Окт. 16, 2024
Key words DYKAT - chiral silicon chlorosilanes silyl ethers isothioureas
Язык: Английский
Synfacts, Год журнала: 2024, Номер 20(11), С. 1201 - 1201
Опубликована: Окт. 16, 2024
Key words DYKAT - chiral silicon chlorosilanes silyl ethers isothioureas
Язык: Английский
Journal of Inorganic and Organometallic Polymers and Materials, Год журнала: 2025, Номер unknown
Опубликована: Фев. 1, 2025
Язык: Английский
Процитировано
6Accounts 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
Процитировано
1Nature 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
Процитировано
0Опубликована: Янв. 1, 2025
Язык: Английский
Процитировано
0Journal of Catalysis, Год журнала: 2025, Номер unknown, С. 116089 - 116089
Опубликована: Март 1, 2025
Язык: Английский
Процитировано
0Chinese 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
Процитировано
0Chemical 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
Процитировано
0Nature 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
Процитировано
0Journal of Catalysis, Год журнала: 2024, Номер 440, С. 115788 - 115788
Опубликована: Окт. 10, 2024
Язык: Английский
Процитировано
2Chemical 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
Процитировано
2