Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(24), P. 17479 - 17646

Published: Oct. 14, 2022

Alkenes and their derivatives are featured widely in a variety of natural products, pharmaceuticals, advanced materials. Significant efforts have been made toward the development new practical methods to access this important class compounds by selectively activating alkenyl C(sp2)–H bonds recent years. In comprehensive review, we describe state-of-the-art strategies for direct functionalization sp2 C–H C–F until June 2022. Moreover, metal-free, photoredox, electrochemical also covered. For clarity, review has divided into two parts; first part focuses on currently available using different alkene as starting materials, second describes bond easily accessible gem-difluoroalkenes material. This includes scope, limitations, mechanistic studies, stereoselective control (using directing groups well metal-migration strategies), applications complex molecule synthesis where appropriate. Overall, aims document considerable advancements, current status, emerging work critically summarizing contributions researchers working fascinating area is expected stimulate novel, innovative, broadly applicable functionalizations coming

Language: Английский

---

Recent advances in chelation-assisted site- and stereoselective alkenyl C–H functionalization

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(5), P. 3263 - 3314

Published: Jan. 1, 2021

Olefinic C-H functionalization represents an atom- and step economic approach to valuable olefin derivatives from simpler ones, but controlling the selectivity remains a challenge. Remarkable progress has been made in site-selective of arenes alkanes, there are still limited examples selective olefins presumably due lability easy decomposition alkenyl moiety. Chelation-assisted activation efficient protocol for site- stereo-selective construction carbon-carbon carbon-heteroatom bonds. This review highlights recent advances vicinal- geminal-group-directed olefinic functionalization, including alkenylation, arylation, alkynylation, alkylation, halogenation, silylation, cyanation annulation by formation exo-/endo-metallocycles. In particular, is covered first time, as well distal-selective under palladium/norbornene cooperative catalysis, which provides novel disconnections retrosynthetic analysis future trend green chemistry.

Language: Английский

---

Application of sulfoxonium ylide in transition-metal-catalyzed C-H bond activation and functionalization reactions

Tetrahedron, Journal Year: 2021, Volume and Issue: 101, P. 132478 - 132478

Published: Oct. 8, 2021

Language: Английский

---

Rh^III-Catalyzed formal [5 + 1] cyclization of 2-pyrrolyl/indolylanilines using vinylene carbonate as a C1 synthon

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(8), P. 1764 - 1769

Published: Jan. 1, 2021

A rhodium(iii)-catalyzed formal C–H [5 + 1] cyclization of 2-pyrrolyl/indolylanilines with vinylene carbonate has been explored towards the potent assembly diverse 4-methylpyrrolo[1,2-a]quinoxalines.

Language: Английский

---

Recent Advances in Metal‐Catalyzed C−H Bond Functionalization Reactions of Sulfoxonium Ylides

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(4)

Published: March 23, 2022

Abstract In recent years, the transition‐metal‐catalyzed functionalization reactions of sulfoxonium ylides have been explored extensively because their usefulness as carbene‐transfer agents, since they can produce metal carbenes through catalysis. Moreover, are safer and advantages simple handling good stability over other counterparts like diazo‐compounds. This review article attempts to highlight advances in metal‐catalyzed C−H ylides.

Language: Английский

---

Iridium-catalyzed B–H insertion of sulfoxonium ylides and borane adducts: a versatile platform to α-boryl carbonyls

Chemical Communications, Journal Year: 2019, Volume and Issue: 56(3), P. 423 - 426

Published: Dec. 4, 2019

Iridium-catalyzed boron-hydrogen bond insertion reactions of trimethylamine-borane and sulfoxonium ylides have been demonstrated, furnishing α-boryl ketones in moderate to excellent yields most cases (51 examples; up 84%). This practical scalable reaction showed broad substrate scope, high functional-group compatibility could be applied late-stage modification structurally complex drug compounds. Further synthetic applications were also demonstrated.

Language: Английский

---

Chemospecific Cyclizations of α‐Carbonyl Sulfoxonium Ylides on Aryls and Heteroaryls

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(45), P. 16198 - 16202

Published: Sept. 11, 2019

The functionalization of aryl and heteroaryls using α-carbonyl sulfoxonium ylides without the help a directing group has remained so far neglected area, despite advantageous safety profile ylides. Described herein are cyclizations onto benzenes, benzofurans N-p-toluenesulfonyl indoles in presence base HFIP, whereas pyrroles N-methyl undergo cyclization an iridium catalyst. Significantly, these two sets conditions chemospecific for each groups substrates.

Language: Английский

---

Synthesis of C6-Substituted Isoquinolino[1,2-b]quinazolines via Rh(III)-Catalyzed C–H Annulation with Sulfoxonium Ylides

The Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 85(5), P. 3192 - 3201

Published: Jan. 16, 2020

We report the synthesis of C6-substituted isoquinolino[1,2-b]quinazolinones via rhodium(III)-catalyzed C–H annulation with sulfoxonium ylides and evaluation cytotoxic activity scaffold. This activation approach enables most straightforward convergent isoquinolino[1,2-b]quinazolines reported to date. operationally simple method is compatible a wide variety ylide arene coupling partners, permitting access diverse isoquinolino[1,2-b]quinazolines. shows high atom economy, generating H2O dimethyl sulfoxide (DMSO) as by-products. scalable operates exquisite N-lactam cyclization selectivity, thus enabling expedient new heterocyclic analogues featuring promising properties.

Language: Английский

---

Copper-Catalyzed Annulation or Homocoupling of Sulfoxonium Ylides: Synthesis of 2,3-Diaroylquinolines or α,α,β-Tricarbonyl Sulfoxonium Ylides

Organic Letters, Journal Year: 2020, Volume and Issue: 22(4), P. 1504 - 1509

Published: Feb. 11, 2020

An unprecedented copper-catalyzed reaction of sulfoxonium ylides and anthranils is reported that enables an easy access to 2,3-diaroylquinolines through a [4+1+1] annulation. Copper-catalyzed homocoupling provided α,α,β-tricarbonyl ylides, which provides strategy extend the carbon chain C–C bond formation. The utility products as well mechanistic details process are presented.

Language: Английский

---

Rhodium(III)-Catalyzed Annulative Coupling of Sulfoxonium Ylides and Allenoates: An Arene C–H Activation/Cyclopropanation Cascade

Organic Letters, Journal Year: 2019, Volume and Issue: 21(22), P. 9217 - 9222

Published: Nov. 5, 2019

Rhodium(III)-catalyzed annulative coupling of sulfoxonium ylides with allenoates was achieved, forming highly functionalized cyclopropanes a quaternary carbon center by means the ylide functionality as traceless bifunctional directing group and C4 synthon via an arene C–H activation cyclopropanation cascade. The protocol features simultaneous formation three new C–C bonds in one pot excellent diastereoselectivity. resultant products could be further transformed to diverse synthetically useful compounds.

Language: Английский

---