Chiral PSiSi‐Ligand Enabled Iridium‐Catalyzed Atroposelective Intermolecular C−H Silylation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(36)

Published: July 18, 2023

Catalytic enantioselective intermolecular C-H silylation offers an efficient approach for the rapid construction of chiral organosilicon compounds, but remains a significant challenge. Herein, new type silyl ligand is developed, which enables first iridium-catalyzed atroposelective reaction 2-arylisoquinolines. This protocol features mild conditions, high atom economy, and remarkable yield with excellent stereoselectivity (up to 99 % yield, ee), delivering enantioenriched axially silane platform molecules facile convertibility. Key success this unprecedented transformation relies on novel PSiSi-ligand, facilitates process perfect chem-, regio- stereo-control via multi-coordinated iridium complex.

Language: Английский

---

Nickel-catalyzed cross-electrophile couplings of aryl fluorosulfates with vinyl chlorosilanes

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 437, P. 115636 - 115636

Published: July 6, 2024

Language: Английский

---

Copper-catalyzed intermolecular Regio- and Enantioselective Hydrosilylation of Alkenes with Prochiral Silanes

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

Published: Jan. 3, 2025

This study presents a copper-catalyzed, substrate-controlled regio- and enantioselective intermolecular hydrosilylation method capable of accommodating broad scope alkenes prochiral silanes. The approach offers an efficient versatile pathway to generate enantioenriched linear branched alkyl-substituted Si-stereogenic Key features this reaction include mild conditions, simple catalytic systems, compatibility with diverse substrates, high yields enantioselectivities. While methods create chiral carbon centers stereochemically defined silicon have been developed, the ability both simultaneously would be value. Here authors present substratecontrolled

Language: Английский

---

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

---

Recyclable Iridium Catalyst Supported on Porous Organic Polymer for Acceptorless Dehydrogenative Silylation: Synthesis of Ring‐Fused Oxasilacycles

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(8), P. 1763 - 1769

Published: March 1, 2024

Abstract The direct conversion of specific C−H bonds to C−Si in alkanes or aromatics via catalytic methods has attracted growing research interest. Herein, we report the preparation a new iridium catalyst supported on naphthyridine‐based porous organic polymer and its successful application dehydrogenative silylation 2‐arylphenols alcohol hydrosilanes access ring‐fused oxasilacycles. synthetic method exhibits broad substrate scope good functional group compatibility while avoiding use hydrogen acceptors. In addition, this could be easily recovered from reaction system reused for at least seven times without apparent deactivation. This provides insights further design heterogeneous nanocatalysts contributes synthesis silicon‐substituted molecules.

Language: Английский

---

Silanes as a versatile hydride source for Ni–H catalysis: a promising tool for π-hydro functionalization

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(15), P. 4290 - 4317

Published: Jan. 1, 2024

Nickel-catalyzed hydrofunctionalization of π-substrates is a possibly effective method to synthesize several value-added molecular architectures. This review covers the NiH catalyzed reactions alkenes, alkynes and allenes.

Language: Английский

---

Axial Ligand Enables Synthesis of Allenylsilane through Dirhodium(II) Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(38)

Published: June 18, 2024

Described herein is a dirhodium(II)-catalyzed silylation of propargyl esters with hydrosilanes, using tertiary amines as axial ligands. By adopting this strategy, range versatile and useful allenylsilanes can be achieved good yields. This reaction not only represents S

Language: Английский

---

Generation of Silicon-Centered Stereogenicity by Chiral Counteranion-Directed Desymmetrization of Silanediols

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(15), P. 10244 - 10247

Published: July 21, 2023

An enantiotopic group-selective monosilylation of silanediols using List's counteranion-directed silylation methodology is reported. A silylium-ion-like silicon electrophile generated from an allylic silane paired with imidodiphosphorimidate (IDPi) enables the enantioselective discrimination two hydroxy groups attached to prochiral atom. The enantioselectivity achieved in desymmetrization step further improved by a subsequent kinetic resolution arrive at silicon-stereogenic disiloxanes high enantiocontrol, along minor amounts achiral trisiloxane byproduct.

Language: Английский

---

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

---

Rare-Earth-Catalyzed Regiodivergent Hydrosilylation of Aryl Alkenes

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 5612 - 5620

Published: March 29, 2024

While transition-metal catalysts have shown the ability to regulate Markovnikov or anti-Markovnikov regioselective hydrosilylation of aryl alkenes, selective control alkenes is still a huge challenge in rare-earth catalyst systems. In this study, we report rare-earth-catalyzed regiodivergent alkenes. Specifically, achieved highly with scandium alkyl complex Cp*AmtBuScCH2SiMe3 (Cp* = pentamethylcyclopentadienyl, AmtBu tBuNC(Me)NtBu, tBu t-butyl) as catalyst. Two key intermediates, e.g., hydride and phenethyl for hydrosilylation, were characterized. Guided by density functional theory (DFT) calculations, successfully inversion using neodymium halide [Cp*AmiPrNdCl]2 (AmiPr iPrNC(Me)NiPr, iPr isopropyl) larger ion radius reduced steric hindrance conjunction LiCH2SiMe3. Interestingly, our study has demonstrated significant influence gradually increasing radii on controlling selectivity reactions, possibly due enlargement coordination space around metal ions. Furthermore, through comparison computational experimental data, observed high level consistency, reaffirming potential calculations predict outcomes providing researchers valuable insights.

Language: Английский

---