Bis(1,1‐dimethylethyl)[2′,4′,6′‐tris‐(1‐methylethyl)[1,1′‐biphenyl]‐2‐yl]‐phosphine and Dicyclohexyl[2′,4′,6′‐tris(1‐methylethyl)[1,1′‐biphenyl]‐2‐yl]phosphine DOI
E. Herrero-Gómez, Antonio M. Echavarren, Ekaterina V. Vinogradova

et al.

Encyclopedia of Reagents for Organic Synthesis, Journal Year: 2021, Volume and Issue: unknown, P. 1 - 17

Published: April 30, 2021

XPhos [564483-18-7] C33H49P (MW 476.72) InChI = 1S/C33H49P/c1-23(2)26-21-30(24(3)4)33(31(22-26)25(5)6)29-19-13-14-20-32(29)34(27-15-9-7-10-16-27)28-17-11-8-12-18-28/h13-14,19-25,27-28H,7-12,15-18H2,1-6H3 InChIKey UGOMMVLRQDMAQQ-UHFFFAOYSA-N (bulky, electron-rich monophosphine used as ligand in transition-metal-catalyzed reactions, especially the context of Pd chemistry) Alternative Names: 2-dicyclohexylphosphino-2′,4′,6′-triisopropyl biphenyl, XPhos. Physical Data: mp 187–190 °C. Solubility: soluble most organic solvents. Form Supplied in: white solid; widely available. t-BuXPhos [564483-19-8] C29H45P 424.65) 1S/C29H45P/c1-19(2)22-17-24(20(3)4)27(25(18-22)21(5)6)23-15-13-14-16-26(23)30(28(7,8)9)29(10,11)12/h13-21H,1-12H3 SACNIGZYDTUHKB-UHFFFAOYSA-N Pd-catalyzed reactions) 2-di-t-butylphosphino-2′,4′,6′-triisopropyl t-BuXPhos, di-t-BuXPhos. 148–151 Handling, Storage, and Precautions: oxidation these related phosphines has been examined.1 The presence three isopropyl groups on 2′, 4′, 6′ positions nonphosphine-containing ring reduces their reactivity toward atmospheric oxygen to less than 3% at room temperature toluene solution after 65 h. Under an atmosphere O2 100 °C for h only 28% 13% phosphine oxide are formed from tert-BuXPhos, respectively. Preparative Method: can be prepared by reaction 2-bromochlorobenzene with Grignard reagent 1-bromo-2,4,6-triisopropylbenzene THF, followed addition catalytic CuCl ClPCy2. A similar procedure using CIPtBu2 was applied synthesis t-BuXPhos.2

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
Enantioselective S−H Insertion Reactions of α‐Carbonyl Sulfoxonium Ylides DOI Creative Commons
Patrícia B. Momo, Alexandria N. Leveille, Elliot H. E. Farrar

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(36), P. 15554 - 15559

Published: April 30, 2020

Abstract The first example of enantioselective S−H insertion reactions sulfoxonium ylides is reported. Under the influence thiourea catalysis, excellent levels enantiocontrol (up to 95 % ee ) and yields 97 %) are achieved for 31 examples in aryl thiols α‐carbonyl ylides.

Language: Английский

Citations

63
Cooperative copper-squaramide catalysis for the enantioselective N–H insertion reaction with sulfoxonium ylides DOI Creative Commons
Lucas G. Furniel, Radell Echemendía, Antonio C. B. Burtoloso

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(21), P. 7453 - 7459

Published: Jan. 1, 2021

The first examples of a highly efficient and enantioselective carbene-mediated insertion reaction, from sulfur ylide, are described.

Language: Английский

Citations

51
Organocatalytic Transformations from Sulfur Ylides DOI Open Access
Marcio Hayashi, Antonio C. B. Burtoloso

Catalysts, Journal Year: 2023, Volume and Issue: 13(4), P. 689 - 689

Published: March 31, 2023

Sulfur ylides are an important class of organic compounds due to their ability perform many different transformations that can give diverse and interesting products with a high degree complexity. Although metal-catalyzed frequent in this compounds, organocatalyzed remain scarce. From initial works, review aims show from sulfur ylides, involving cyclopropanation formal N–H, S–H, C–H insertion reactions, including enantioselective versions. The proposed mechanisms the modes activation these organocatalysts will be covered. Furthermore, advances area potential challenges circumvented near future also discussed.

Language: Английский

Citations

13
Recent advance: Sulfur ylides in organic synthesis DOI
M. Kumar,

Ifrah Sadaf,

Jyotsna Pamidighantam

et al.

Journal of Heterocyclic Chemistry, Journal Year: 2023, Volume and Issue: 61(1), P. 29 - 70

Published: Oct. 26, 2023

Abstract Sulfur ylides are versatile structures that display various characteristics and participate in a myriad of reactions to produce simple, effective, sometimes stereoselective toward synthesizing sulfur‐containing compounds. Nonetheless, their fulfillment tremendous developments have been made this field the past few decades. In comprehensive review, luminosity is illuminated on application sulfur involved domino, cascade annulation reactions, carbene trapping reagents with chameleonic reactivity. numerous decennary, chemists used solvent‐dependent, rhodium catalyzed, dealkylative intercepted, photochemical reaction, halotrifluoromethylation, benzannulation, amidation name such as Mizoroki–Heck, Suzuki–Miyaura, Sommelet–Hauser rearrangements. Moreover, other prime applications include metal catalysis, epoxidation carbonyl compounds, acylmethylation, cyclomerization, oxidation, insertion reactions. Additionally, some extremely useful play major role synthesis medicinally active heterocycles structural motifs. This review article discusses all these proposed mechanisms, current scenario, at length. tutorial concludes by providing future outlook investigation into compounds synthesized using it great potential be industries, laboratories, pharmaceutical companies, drug production, clinical use, medicinal chemistry, agrochemical purposes.

Language: Английский

Citations

11
Recent Developments in Stereoselective Reactions of Sulfoxonium Ylides DOI Creative Commons

Ciarán O’Shaughnessy,

Mukulesh Mondal,

Nessan J. Kerrigan

et al.

Molecules, Journal Year: 2025, Volume and Issue: 30(3), P. 655 - 655

Published: Feb. 1, 2025

This review probes the recent developments in stereoselective reactions within area of sulfoxonium ylide chemistry since early 2000s. An abundance research has been applied to its emergence 1960s. There a continued effort then with work traditional areas, such as epoxidation, aziridination and cyclopropanation. Efforts have also novel olefination insertion reactions, develop methodologies using organocatalysis transition metal catalysis. The growing interrupted Johnson–Corey–Chaykovsky is described, whereby unexpected cyclopropanation epoxidation developed. In general, most observed mechanistic pathway ylides formal cycloaddition: (2 + 1) (e.g., epoxides, cyclopropanes, aziridines), (3 oxetanes, azetidines), (4 indanones, indolines). involves formation zwitterionic intermediate through nucleophilic addition carbanion an electrophilic site. intramolecular cyclization occurs, constructing cyclic product. Insertion X–H bonds X = S, N or P) are observed, protonation followed by X, form inserted

Language: Английский

Citations

0
Divergent Synthesis of Dihydrofuran and Dienol Scaffolds via Pd-Catalyzed Decarboxylative Carbene Cross-Coupling DOI
Xiaolong Ma,

Erfei Miao,

Yili Sun

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

Herein, we report a novel ligand-switchable Pd-catalyzed carbene coupling reaction employing vinylethylene carbonates and sulfoxonium ylides. By proper choice of ligands, the chemoselectivity process could be efficiently regulated, allowing for availability dihydrofuran or dienol scaffolds. This method features mild conditions, broad scope, remarkable synthetic utility. Compound 6f can effectively stimulate secretion GLP-1, providing promising insight into development small-molecule agonists GLP-1 receptor.

Language: Английский

Citations

0
Cyclic Sulfoxonium Ylides: Synthesis and Chemospecific Reactivity in the Catalytic Alkylation of Indoles DOI
Clarice A. D. Caiuby, Lucas Vidal, Antonio C. B. Burtoloso

et al.

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(7)

Published: Feb. 7, 2023

Abstract The study of the reactivity cyclic sulfoxonium ylides has been so far neglected, in particular for reactions that forms carbon‐carbon bond at ylide carbon atom. Herein, we describe synthesis by palladium‐catalyzed intramolecular arylation and these C3‐alkylation indoles presence either an acid catalyst or iridium catalyst. This revealed catalysis is only efficient which tether a six‐membered lactone, whereas was better suited to reaction five‐membered ring ketone lactone. observed chemospecificity might be due relative basicity under steric hindrance around carbene intermediate when conducted with

Language: Английский

Citations

10
Pd/C-Catalyzed Carbonylative Synthesis of α-Carbonyl-α′-Amide Sulfoxonium Ylides from Azides DOI
Yang Yuan, Bo Chen, Youcan Zhang

et al.

The Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 85(8), P. 5733 - 5740

Published: March 25, 2020

The synthesis of α-carbonyl-α′-amide sulfoxonium ylides by Pd/C-catalyzed carbonylative transformation azides with α-carbonyl has been studied. This method offers a direct approach to produce synthetically useful in high efficiency. By using readily available substrates, 39 examples products were prepared good yields outstanding functional group compatibility. An example converting the obtained ylide into corresponding 1,3-dicarbonyl compound given as well.

Language: Английский

Citations

22
The α-alkylation of carbonyl sulfoxonium ylides: studies and applications in the synthesis of new sulfur heterocycles DOI
Matheus Pereira de Jesus, Radell Echemendía, Antonio C. B. Burtoloso

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(14), P. 3577 - 3584

Published: Jan. 1, 2023

α-Alkylation of carbonyl sulfoxonium ylides.

Language: Английский

Citations

8