146475-56-1Relevant academic research and scientific papers
A general method for palladium-catalyzed reactions of primary sulfonamides with aryl nonaflates
Shekhar, Shashank,Dunn, Travis B.,Kotecki, Brian J.,Montavon, Donna K.,Cullen, Steven C.
, p. 4552 - 4563 (2011/07/31)
A general method for Pd-catalyzed sulfonamidation of aryl nonafluorobutanesulfonates (aryl nonaflates) is described. A biaryl phosphine ligand, t-BuXPhos, formed the most active catalyst, and K3PO 4 in tert-amyl alcohol was found to be the optimal base-solvent combination for the reaction. The reaction conditions were tolerant of various functional groups such as cyano, nitro, ester, aldehyde, ketone, chloride, carbamate, and phenol. Heterocyclic aryl nonaflates were found to be suitable coupling partners. High yields of the coupled products were obtained from the reactions between inherently disfavored substrates such as electron-rich nonaflates and electron-poor sulfonamides. Kinetic data suggest reductive elimination to be the rate-limiting step for the reaction. The only limitation of this methodology that we have identified is the inability of 2,6-disubstituted aryl nonaflates to efficiently participate in the reaction.
Mild Pd-catalyzed N -arylation of methanesulfonamide and related nucleophiles: Avoiding potentially genotoxic reagents and byproducts
Rosen, Brandon R.,Ruble, J. Craig,Beauchamp, Thomas J.,Navarro, Antonio
supporting information; experimental part, p. 2564 - 2567 (2011/06/25)
A convenient, general, and high yielding Pd-catalyzed cross-coupling of methanesulfonamide with aryl bromides and chlorides is reported. The use of this method eliminates concern over genotoxic impurities that can arise when an aniline is reacted with methanesulfonyl chloride. The application of this method to the synthesis of dofetilide is also reported.
Cyclopropanesulfonyl Chloride: Its Mechanism of Hydrolysis and Reactions with Tertiary Amines in Organic Media
King, James F.,Lam, Joe Y. L.,Ferrazzi, Gabriele
, p. 1128 - 1135 (2007/10/02)
Cyclopropanesulfonyl chloride (1) has been synthesized and its reactions examined to see if the three-membered ring leads to unusual reactions in either 1 or the corresponding sulfene, cyclopropanethione S,S-dioxide (2). pH-rate profiles, primary kinetic isotope effects (KIE's), and pH-product ratio experiments are in full agreement with mechanisms of hydrolysis of 1 like those of a simple alkanesulfonyl chlorides (J.Am.Chem.Soc.1992,114,1743-1749), specifically, (a) below pH 7.2 by SN2-S reaction with water and (b) above pH 7.3, elimination by hydroxide to form the sulfene (2) which is trapped by (i) water below pH 12.0 and (ii) hydroxide above pH 12.0.The products of the reaction of cyclopropanesulfonyl-1-d chloride (9) with triethylamine and 2-propanol in dichloromethane indicate that most of the reaction goes via 2; the analogous reaction with trimethylamine apparently proceeds by a direct formation of the sulfonylammonium chloride (14) which then yields the α-deuterated N,N-dimethyl sulfonamide (12, R=Me).The evident sulfene formation processes in the reaction of triethylamine with ethenesulfonyl, 2-propanesulfonyl, and cyclopropanesulfonyl chlorides show very low primary KIE's (1.5), pointing to highly product-like transition states.Reaction of 1 with an enamine (1-pyrrolidino-2-methylpropene, 20) in the presence of a base in either water or dichloromethane gave cyclopropanesulfonpyrrolidide (23) and an aldehyde adduct (24), but no four-membered cycloadduct (21).
