β‐Diazocarbonyl Compounds: Synthesis and their Rh(II)‐Catalyzed 1,3 C−H Insertions DOI
Liyin Jiang, Zhaofeng Wang,

Melanie Armstrong

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(11), P. 6177 - 6184

Published: Dec. 4, 2020

Abstract Herein, we describe the first electrophilic diazomethylation of ketone silyl enol ethers with diazomethyl‐substituted hypervalent iodine reagents that gives access to unusual β‐diazocarbonyl compounds. The potential this unexplored class diazo compounds for development new reactions was demonstrated by discovery a rare Rh‐catalyzed intramolecular 1,3 C−H carbene insertion led complex cyclopropanes excellent stereocontrol.

Language: Английский

Late-stage diversification of indole skeletons through nitrogen atom insertion DOI
Julia C. Reisenbauer, Ori Green, Allegra Franchino

et al.

Science, Journal Year: 2022, Volume and Issue: 377(6610), P. 1104 - 1109

Published: Sept. 1, 2022

Compared with peripheral late-stage transformations mainly focusing on carbon-hydrogen functionalizations, reliable strategies to directly edit the core skeleton of pharmaceutical lead compounds still remain scarce despite recent flurry activity in this area. Herein, we report skeletal editing indoles through nitrogen atom insertion, accessing corresponding quinazoline or quinoxaline bioisosteres by trapping an electrophilic nitrene species generated from ammonium carbamate and hypervalent iodine. This reactivity relies strategic use a silyl group as labile protecting that can facilitate subsequent product release. The utility highly functional group-compatible methodology context several commercial drugs is demonstrated.

Language: Английский

Citations

211
Carbon Atom Insertion into Pyrroles and Indoles Promoted by Chlorodiazirines DOI Creative Commons
Balu D. Dherange, Patrick Q Kelly, Jordan P. Liles

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(30), P. 11337 - 11344

Published: July 21, 2021

Herein, we report a reaction that selectively generates 3-arylpyridine and quinoline motifs by inserting aryl carbynyl cation equivalents into pyrrole indole cores, respectively. By employing α-chlorodiazirines as thermal precursors to the corresponding chlorocarbenes, traditional haloform-based protocol central parent Ciamician-Dennstedt rearrangement can be modified directly afford 3-(hetero)arylpyridines quinolines. Chlorodiazirines are conveniently prepared in single step oxidation of commercially available amidinium salts. Selectivity function substitution pattern was examined, predictive model based on steric effects is put forward, with DFT calculations supporting selectivity-determining cyclopropanation step. Computations surprisingly indicate stereochemistry little consequence subsequent electrocyclic ring opening forges pyridine core, due compensatory homoaromatic stabilization counterbalances orbital-controlled torquoselectivity effects. The utility this skeletal transform further demonstrated through preparation quinolinophanes editing pharmaceutically relevant pyrroles.

Language: Английский

Citations

184
Dearomative ring expansion of thiophenes by bicyclobutane insertion DOI
Huamin Wang, Huiling Shao, Ankita Das

et al.

Science, Journal Year: 2023, Volume and Issue: 381(6653), P. 75 - 81

Published: July 6, 2023

Skeletal ring enlargement is gaining renewed interest in synthetic chemistry and has recently focused on insertion of one or two atoms. Strategies for heterocyclic expansion through small-ring remain elusive, although they would lead to the efficient formation bicyclic products. Here, we report a photoinduced dearomative thiophenes by bicyclo[1.1.0]butanes produce eight-membered rings under mild conditions. The value, broad functional-group compatibility, excellent chemo- regioselectivity were demonstrated scope evaluation product derivatization. Experimental computational studies point toward photoredox-induced radical pathway.

Language: Английский

Citations

118
Ring expansion of indene by photoredox-enabled functionalized carbon-atom insertion DOI
Fu‐Peng Wu, Chetan C. Chintawar, Rémy F. Lalisse

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(3), P. 242 - 251

Published: Jan. 9, 2024

Language: Английский

Citations

39
Regiodivergent Ring-Expansion of Oxindoles to Quinolinones DOI Creative Commons

Hendrik L. Schmitt,

Den Martymianov,

Ori Green

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(7), P. 4301 - 4308

Published: Feb. 9, 2024

The development of divergent methods to expedite structure–activity relationship studies is crucial streamline discovery processes. We developed a rare example regiodivergent ring expansion access two regioisomers from common starting material. To enable this regiodivergence, we identified distinct reaction conditions for transforming oxindoles into quinolinone isomers. presented proved be compatible with variety functional groups, which enabled the late-stage diversification bioactive as well facilitated synthesis drugs and their derivatives.

Language: Английский

Citations

20
Dirhodium(II,II) Paddlewheel Complexes DOI
Radim Hrdina

European Journal of Inorganic Chemistry, Journal Year: 2021, Volume and Issue: 2021(6), P. 501 - 528

Published: Jan. 7, 2021

Abstract This minireview summarizes synthetic approaches towards homoleptic dirhodium(II,II) paddlewheel complexes with the general formula Rh 2 A 4 . These have found numerous applications in a wide range of chemical research and industry as catalysts, detectors, enzymatic inhibitors or building blocks for molecular scaffolds. In organic synthesis they are commonly used to transfer electron‐deficient species, act Lewis acids activate unsaturated bonds, serve hydrogenation catalysts participate oxidation/reduction processes. Dirhodium composed Rh‐Rh backbone four bridging anions, which surround core. According application, electrochemical potential atom can be modulated, geometry physical properties metal complex. prepared one step from basic inorganic precursors by post‐functionalization structures.

Language: Английский

Citations

61
Convergent Synthesis of 1,4-Dicarbonyl Z-Alkenes through Three-Component Coupling of Alkynes, α-Diazo Sulfonium Triflate, and Water DOI

Xuyong Wang,

Wen‐Yan Tong,

Bing Huang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(11), P. 4952 - 4965

Published: March 11, 2022

We report a general protocol for the convergent synthesis of 1,4-dicarbonyl Z-alkenes form alkynes using α-diazo sulfonium triflate and water. The C═O, C═C, C–H bonds are formed under mild conditions with wide range functional groups tolerated. reaction exhibits excellent Z-selectivity complete regioselectivity. resulting can smoothly undergo follow-up conversion to variety heteroaromatic scaffolds. Moreover, also provides facile access corresponding deuterated heteroarenes high level deuterium incorporation (90–97% D-inc.) by directly D2O, thus rendering method highly valuable. comprehensive mechanistic studies indicate that free carbyne radical intermediate is via photocatalytic single electron transfer process, KH2PO4 plays crucial role in significant improvements on yield selectivity based density-functional theory calculations, providing new direction coupling reactions diazo compounds.

Language: Английский

Citations

52
Generating Fischer-Type Rh-Carbenes with Rh-Carbynoids DOI Creative Commons

Eric Palomo,

Akhilesh K. Sharma, Zhaofeng Wang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(9), P. 4975 - 4981

Published: Feb. 22, 2023

We describe the first catalytic generation of Fischer-type acyloxy Rh(II)-carbenes from carboxylic acids and Rh(II)-carbynoids. This novel class transient donor/acceptor evolved through a cyclopropanation process providing access to densely functionalized cyclopropyl-fused lactones with excellent diastereoselectivity. DFT calculations allowed analysis properties Rh(II)-carbynoids as well characterization mechanism.

Language: Английский

Citations

32
Recent Progress in Synthetic Applications of Cyclic Hypervalent Iodine(III) Reagents DOI Creative Commons
Akira Yoshimura, Akio Saito, Viktor V. Zhdankin

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(16), P. 2653 - 2675

Published: April 21, 2023

Abstract Hypervalent iodine compounds have found broad application in modern organic chemistry as reagents and catalysts. Cyclic hypervalent based on the benziodoxole heterocyclic system higher stability compared to their acyclic analogues, which makes possible preparation safe handling of with special ligands such azido, cyano, trifluoromethyl groups. Numerous iodine‐substituted derivatives been prepared utilized for transfer substituent substrate. Reactions these substrates can be performed under metal‐free conditions, presence transition metal catalysts, or using photocatalysts photoirradiation conditions. In this review, we focus most recent synthetic applications cyclic iodine(III) following ligands: N 3 , NHR, CN, CF SCF OR, OAc, ONO 2 C(=N )CO R. The review covers literature published mainly last 5 years.

Language: Английский

Citations

30
Enantioselective Multifunctionalization with Rh Carbynoids DOI
Yu Qian,

Jie Tang,

Xiaoyu Zhou

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(48), P. 26403 - 26411

Published: Nov. 22, 2023

Multifunctionalization from the interception of active intermediates is an attractive synthetic strategy for efficient construction complex molecular scaffolds in atom and step economic fashion. However, design reactions involving metal carbynoids that exhibit carbene/carbocation behavior currently limited, developing catalyst-controlled highly enantioselective versions poses significant challenges. In this study, we present first asymmetric trifunctionalization with rhodium carbynoids. This reaction unveils distinctive reactivity carbynoid precursor, enabling it to react simultaneously two nucleophiles one electrophile. process involves formation distinct carbene ylides alcohol/carbamate trapping ylide imine, resulting three new bonds. Furthermore, allows divergent synthesis a wide array β-amino esters high yields exceptional enantioselectivity.

Language: Английский

Citations

25