Conformational Locking Induced Enantioselective Diarylcarbene Insertion into B−H and O−H Bonds Using a Cationic Rh(I)/Diene Catalyst DOI

Weici Xu,

Takeshi Yamakawa,

Meiling Huang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(45)

Published: July 18, 2024

Abstract Transition‐metal‐catalyzed enantioselective transformations of aryl/aryl carbene are inherently challenging due to the difficulty in distinguishing between two arene rings reaction process thus remain largely less explored. The few successful examples reported so far, without exception, have all been catalyzed by Rh(II)‐complexes. Herein, we describe our development a novel cationic Rh(I)/chiral diene catalytic system capable efficient B−H and O−H insertions with diaryl diazomethanes, allowing access broad range gem ‐diarylmethine boranes ethers good yields high enantioselectivities. Notably, previously unattainable asymmetric diarylcarbene insertion into bond was achieved for first time. A remarkable feature this newly designed Rh(I)/diene catalyst bearing ortho ‐amidophenyl substitutents is that it can distinguish through stereochemically selective control π–π stacking interactions. DFT calculations indicate rotation‐restricted conformation complex played an important role highly transformations. This work provides interesting unprecedented stereocontrol mode metal

Language: Английский

Transition Metal Catalyzed Insertion Reactions with Donor/Donor Carbenes DOI
Benjamin D. Bergstrom, Leslie A. Nickerson, Jared T. Shaw

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(13), P. 6864 - 6878

Published: Aug. 8, 2020

Donor/donor carbenes are relatively new in the field of carbene chemistry; although applications C-H and X-H insertion reactions few number, they demonstrate exquisite chemo- stereo-selectivity. Recent reports have shown that C-H, N-H, B-H, O-H, S-H, Si-H, Ge-H, Sn-H P-H feasible with a variety transition metal catalysts, both inter- intramolecularly. Furthermore, high degrees diastereo- enantioselectivity been observed several cases. Methods typically involve formation diazo-based precursor, but procedures using diazo-free developed significant success. This Minireview covers transition-metal catalyzed donor/donor donor carbenes, providing context for future developments this emerging field.

Language: Английский

Citations

157
Photochemical Carbene Transfer Reactions of Aryl/Aryl Diazoalkanes—Experiment and Theory** DOI
Sripati Jana, Chao Pei, Claire Empel

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(24), P. 13271 - 13279

Published: March 9, 2021

Controlling the reactivity of carbene intermediates is a key parameter in development selective transfer reactions and usually achieved by metal complexes via singlet metal-carbene intermediates. In this combined experimental computational studies, we show that free diaryl carbenes can be controlled electronic properties substituents without need external additives. The introduction electron-donating -withdrawing groups results significant perturbation triplet energy splitting intermediate activation energies consecutive reactions. This strategy now overcomes long-standing paradigm allows realization highly chemoselective with alkynes. We could readily accessed photolysis corresponding diazo compounds these undergo cyclopropenation, cascade, or C-H functionalization Experimental theoretical mechanistic analyses confirm participation different spin states rationalize for observed reactivity.

Language: Английский

Citations

91
Enantioselective Insertion of Alkynyl Carbenes into Si–H Bonds: An Efficient Access to Chiral Propargylsilanes and Allenylsilanes DOI
Liang‐Liang Yang,

Jing Ouyang,

Hui-Na Zou

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(17), P. 6401 - 6406

Published: April 27, 2021

Chiral propargylsilanes and chiral allenylsilanes have emerged as versatile building blocks for organic synthesis. However, efficient methods preparing these organosilicon compounds are lacking. We herein report a highly enantioselective method synthesis of from readily available alkynyl sulfonylhydrazones. Specifically, spiro phosphate dirhodium complexes were used to catalyze asymmetric insertion carbenes into the Si–H bonds silanes afford variety with excellent enantioselectivity. Subsequently, platinum catalyst was stereospecific isomerization corresponding allenylsilanes.

Language: Английский

Citations

81
Regiospecific and Enantioselective Arylvinylcarbene Insertion of a C–H Bond of Aniline Derivatives Enabled by a Rh(I)-Diene Catalyst DOI

Dong‐Xing Zhu,

Hui Xia, Jianguo Liu

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(6), P. 2608 - 2619

Published: Feb. 4, 2021

Asymmetric insertion of an arylvinylcarbenoid into the C–H bond for direct enantioselective C(sp2)-H functionalization aniline derivatives catalyzed by a rhodium(I)-diene complex was developed first time. The reaction occurred exclusively at uncommon vinyl terminus site with excellent E selectivity and enantioselectivities, providing various chiral γ,γ-gem-diarylsubstituted α,β-unsaturated esters broad functional group compatibility under simple mild conditions. It provides rare example asymmetric arenes selective vinylogous reactivity. Synthesis applications this protocol were featured several versatile product transformations. Systematic DFT calculations also performed to elucidate mechanism origin enantio- regioselectivity Rh(I)-catalyzed reaction. measured computed inverse deuterium kinetic isotope effect supports C–C bond-formation step as rate-determining step. Attractive interactions between ligand substrates proposed control enantioselectivity.

Language: Английский

Citations

71
Highly Atroposelective Rhodium(II)-Catalyzed N–H Bond Insertion: Access to Axially Chiral N-Arylindolocarbazoles DOI
Qiao Ren, Tingting Cao, Chun‐Nian He

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(10), P. 6135 - 6140

Published: May 6, 2021

The highly atroposelective construction of axially chiral N-arylindolocarbazoles is disclosed via the Rh(II)-catalyzed intermolecular carbene N–H insertion reactions. This straightforward transformation provides a rapid access to wide range enantio-enriched N-arylindolocarbazole atropisomers bearing C–N axis in moderate good yields and high enantioselectivities. Also, synthetic utility this protocol unambiguously emphasized by late-stage functionalization (LSF) some representative natural products bioactive molecules. Furthermore, polyaromatic ring N-arylindolocarbazole-derived phosphoric acid (CPA) synthesis also highlight its practical value materials chemistry catalytic asymmetric synthesis.

Language: Английский

Citations

61
Catalytic asymmetric silicon-carbon bond-forming transformations based on Si-H functionalization DOI Open Access
Li Li, Wei‐Sheng Huang, Zheng Xu

et al.

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

Published: May 4, 2023

Language: Английский

Citations

37
Construction of Ge-Stereogenic Center by Desymmetric Carbene Insertion of Dihydrogermanes DOI

Ai‐Cui Han,

Li‐Jun Xiao, Qi‐Lin Zhou

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5643 - 5649

Published: Feb. 8, 2024

We developed a method for the enantioselective synthesis of germanium-stereogenic compounds by desymmetric carbene insertion dihydrogermanes. A chiral rhodium phosphate catalyst decomposes diaryldiazo-methanes to generate carbenes that insert enantioselectively into one two Ge–H bonds dihydrogermanes form under mild reaction conditions. By this method, variety germanes with centers were synthesized in high yields and excellent enantioselectivities. Kinetic studies showed diazo decomposition process was rate-determining step. The remaining bond germane products provides possibility preparing tetra-substituted compounds.

Language: Английский

Citations

12
Mechanistically Guided Workflow for Relating Complex Reactive Site Topologies to Catalyst Performance in C–H Functionalization Reactions DOI
Ryan C. Cammarota, Wenbin Liu, John Bacsa

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(4), P. 1881 - 1898

Published: Jan. 24, 2022

Leveraging congested catalyst scaffolds has emerged as a key strategy for altering innate substrate site-selectivity profiles in C-H functionalization reactions. Similar to enzyme active sites, optimal small molecule catalysts often feature reactive cavities tailored controlling approach trajectories. However, relating three-dimensional shape reaction output remains formidable challenge, part due the lack of molecular features capable succinctly describing complex site topologies terms numerical inputs machine learning applications. Herein, we present new set descriptors, "Spatial Molding Approachable Rigid Targets" (SMART), which have applied quantify spatial constraints an expansive library dirhodium and predict 1-bromo-4-pentylbenzene via donor/acceptor carbene intermediates. Optimal terminal methylene position was obtained with Rh2(S-2-Cl-5-MesTPCP)4 (30.9:1 rr, 14:1 dr, 87% ee), while at electronically activated benzylic increasingly favored Rh2(TPCP)4 lacking ortho-Cl, Rh2(S-PTAD)4, Rh2(S-TCPTAD)4, respectively. Intuitive global models 25 disparate were developed multivariate linear regression explicitly assess contributing roles steric congestion dirhodium-carbene electrophilicity functionalization. The workflow utilizes classification extract descriptors only conformers, nuance that may be widely applicable establishing close correspondence between ground-state model systems transition states. Broader still, SMART are amenable delineating salient reactivity other chemical biological contexts.

Language: Английский

Citations

31
Pd/Ming-Phos-Catalyzed Asymmetric Three-Component Arylsilylation of N-Sulfonylhydrazones: Enantioselective Synthesis of gem-Diarylmethine Silanes DOI
Bin Yang,

Kangning Cao,

Guofeng Zhao

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(34), P. 15468 - 15474

Published: Aug. 22, 2022

A Pd-catalyzed enantioselective three-component reaction of N-sulfonylhydrazones, aryl bromides, and silylboronic esters is developed, enabling the synthesis chiral gem-diarylmethine silanes in high enantioselectivity with use a newly identified Ming-Phos. Compared N-tosyl, more easily decomposed N-mesitylsulfonyl suitable as masking group electron-rich hydrazone to improve efficiency. The features broad scope concerning both coupling partners, enantioselectivity, mild conditions. ready access enantiomers utility this catalytic method are also presented.

Language: Английский

Citations

29
Chiral organophosphates as ligands in asymmetric metal catalysis DOI Creative Commons

Nikolai Brodt,

Jochen Niemeyer

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(12), P. 3080 - 3109

Published: Jan. 1, 2023

Chiral phosphates have successfully been used as ligands in asymmetric metal-catalysis. This Minireview discusses the most recent examples, including main-group catalysis, transition-metal catalysis and by rare-earth metals.

Language: Английский

Citations

18