Palladium-Catalyzed Synthesis of α-Carbonyl-α′-(hetero)aryl Sulfoxonium Ylides: Scope and Insight into the Mechanism DOI

Christopher Janot,

Jean-Baptiste Chagnoleau,

Nathan R. Halcovitch

et al.

The Journal of Organic Chemistry, Journal Year: 2019, Volume and Issue: 85(2), P. 1126 - 1137

Published: Dec. 6, 2019

Despite recent advances, a general method for the synthesis of α-carbonyl-α′-(hetero)aryl sulfoxonium ylides is needed to benefit more greatly from potential safety advantages offered by these compounds over parent diazo compounds. Herein, we report palladium-catalyzed cross-coupling aryl bromides and triflates with α-carbonyl ylides. We also use this modification an active pharmaceutical ingredient key precursor antagonists neurokinin-1 receptor. In addition, mechanism reaction was inferred several observations. Thus, oxidative addition complex [(XPhos)PhPdBr] its dimer were observed 31P{1H} NMR, complexes shown be catalytically kinetically competent. Moreover, resulting transmetalation [(XPhos)ArPdBr] (Ar = p-CF3–C6H4) model ylide mass spectrometry. Finally, partial rate law suggests that subsequent deprotonation are rate-determining in catalytic cycle.

Language: Английский

Asymmetric transformations from sulfoxonium ylides DOI Creative Commons
Clarice A. D. Caiuby, Lucas G. Furniel, Antonio C. B. Burtoloso

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 13(5), P. 1192 - 1209

Published: Dec. 8, 2021

Sulfoxonium ylides are important surrogates for diazo compounds, and their use in industry as safer alternatives has been evaluated during recent years. Beyond the known classical transformations, these have also used a surprising plethora of novel intrinsic chemical reactions, especially Bench stability handling an advantage this class organosulfur molecules. Despite this, efficient asymmetric specifically catalytic enantioselective versions, only recently reported, there specific reasons this. This perspective article covers topic from first studies up to latest advances, giving personal perspectives showing main challenges area coming

Language: Английский

Citations

94
Recent Advances in Metal‐Catalyzed C−H Bond Functionalization Reactions of Sulfoxonium Ylides DOI

Pratiksha Bhorali,

Sabera Sultana, Sanjib Gogoi

et al.

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

Citations

41
Iridium-catalyzed B–H insertion of sulfoxonium ylides and borane adducts: a versatile platform to α-boryl carbonyls DOI
Shang‐Shi Zhang, Hui Xie, Bing Shu

et al.

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

Citations

74
Chemospecific Cyclizations of α‐Carbonyl Sulfoxonium Ylides on Aryls and Heteroaryls DOI Creative Commons

Daniel Clare,

Benjamin C. Dobson,

Phillip A. Inglesby

et al.

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

Citations

69
Synthesis of C6-Substituted Isoquinolino[1,2-b]quinazolines via Rh(III)-Catalyzed C–H Annulation with Sulfoxonium Ylides DOI
Jin Zhang, Xiaogang Wang, Di Chen

et al.

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

Citations

67
Copper-Catalyzed Annulation or Homocoupling of Sulfoxonium Ylides: Synthesis of 2,3-Diaroylquinolines or α,α,β-Tricarbonyl Sulfoxonium Ylides DOI
Shuai Zhu, Kai Shi, Hao Zhu

et al.

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

Citations

61
Rhodium(III)-Catalyzed Annulative Coupling of Sulfoxonium Ylides and Allenoates: An Arene C–H Activation/Cyclopropanation Cascade DOI
Jiang Lou, Quannan Wang, Yong‐Gui Zhou

et al.

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

Citations

59
Ruthenium-Catalyzed Chemoselective N–H Bond Insertion Reactions of 2-Pyridones/7-Azaindoles with Sulfoxonium Ylides DOI
Xiaofeng Liu, Ying Shao, Jiangtao Sun

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(3), P. 1038 - 1043

Published: Jan. 21, 2021

A ruthenium-catalyzed highly chemoselective N-alkylation of 2-pyridones has been developed, affording N-alkylated 2-pyridone derivatives in good yields and excellent N-selectivity. The key to achieve this unprecedented N–H rather than O–H insertion reaction is the use CpRu(PPh3)2Cl as catalyst sulfoxonium ylides alkylation reagents. Moreover, protocol also amenable 7-azaindoles by slightly varying conditions. Furthermore, sulfonium are suitable reagents, providing selectivity.

Language: Английский

Citations

49
Rh(iii)-catalyzed C–H annulation of sulfoxonium ylides with iodonium ylides towards isocoumarins DOI
Chuanliu Yin, Lianghao Li, Chuanming Yu

et al.

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(5), P. 1112 - 1116

Published: Jan. 1, 2022

The direct synthesis of isocoumarin skeletons has been realized through the Rh( iii )-catalyzed [3 + 3] annulation sulfoxonium ylides and iodonium under mild conditions.

Language: Английский

Citations

33
Synthesis of α-Carbonyl-α′-amide Sulfoxonium Ylides from Isocyanates with Complete Atom Economy DOI

Ajay Kant Gola,

Ajay Sharma, Satyendra Kumar Pandey

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(7), P. 1214 - 1217

Published: Feb. 9, 2023

An efficient catalyst- and additive-free facile synthesis of α-carbonyl-α′-amide sulfoxonium ylides from isocyanates β-ketosulfoxonium with complete atom economy has been described. The adorned various functional groups were well-tolerated afforded moderate to high yields the ylide derivatives. Finally, using large-scale reactions converting synthesized into other valuable compounds, we demonstrated practicality this synthetic method.

Language: Английский

Citations

18