Synthesis of Sultams by Intramolecular Heck Reaction

Abstract

A novel access to a-methylene-g-sultams via the intramolecular Heck reaction of a-bromovinylsulfonamides derived from allylic amines is reported. These heterocycles are potent Michael acceptors towards sulfur nucleophiles.

Synthesis of a Library of 1,5,2-Dithiazapine 1,1-Dioxides. Part 2: Routes to Bicyclic Sultams

“…10,11 The reported methodologies for other non-benzofused bicyclic sultams include Diels-Alder reaction, 12 1,3-dipolar cycloaddition, 13 Pauson Khand cyclization, 14 RCM, 15 Heck-type cyclization, 16 oxa-Michael and Baylis-Hillman reaction, 17 as well as oxidation from isothiazole. 18 In this regard, we sought simple installation of an additional ring to the previously reported 1,5,2-dithiazepine 1,1-dioxide scaffolds in order to enrich our collection of sultam chemotypes.…”

Bis[tri(o-tolyl)phosphine]palladium

“…28 Intramolecular Heck reactions of α-bromo-vinylsulfonamides have been shown to yield α-methylene-γ-sultams. 29 Numerous polymers have been prepared through the use of Heck coupling reactions. 30 For example, poly(p-phenylenevinylene)s (PPVs) with a dendritic phenylazomethine (DPA) as a metalcollecting site were synthesized via the Heck reaction by filling the coordination site of the DPA moiety via complexation with rare earth metal ions.…”

Stereoselective preparation of γ- and σ-sultams by thermal and high-pressure intramolecular Diels–Alder reaction of vinylsulfonamides

“…3 Recently developed powerful methodologies for the generation of these cyclic sulfonamides include the intramolecular Diels-Alder reaction, 4 sulfonamide dianion alkylation, 5 radical cyclization, 6 ringclosing metathesis, 7 and intramolecular Heck cyclization. 8 In two previous communications, 4a,b we reported the efficient preparation of five-and six-membered sultams by thermal-and highpressure intramolecular [4+2] cycloadditions of vinylsulfonamides possessing an acyclic, furan or carbocyclic 1,3-diene moiety. Here we give a full account on these studies including the concise preparation of enantiomerically pure δ-sultams that can be applied as novel chiral auxiliaries.…”