Aromatic Allylsulfenylation with in Situ Generated Allyl Thiols under the Heck Conditions

Abstract

By the catalysis of palladium(0), S-allyl thiocarbamates 1 react with aryl iodides and vinyl bromides to give allyl aryl sulfides and allyl vinyl sulfides, respectively, in good yields.

Fe(II)-Catalyzed Imidation of Allyl Sulfides and Subsequent [2,3]-Sigmatropic Rearrangement. Preparation of α-Branched N-tert-Butyloxycarbonyl (Boc)-Protected N-Allylamines

“…In addition, the anisyl (An = p -methoxyphenyl) analogue 5 of compound 1a was prepared by the very same method starting from p -methoxythiophenol (eq 2). Reduction of ester 1d with Dibal-H in hexane yielded the alcohol 1b in 46% yield.…”

“…2-Butenyl p -Methoxyphenyl Sulfide (5). As described in typical procedure A, the reaction of 0.25 g of sodium (10 mmol), 1.2 mL of p -methoxythiophenol (1.4 g, 10 mmol), and 1.4 g of crotyl bromide (10 mmol) was carried out at room temperature (reaction time: 2 h). The crude product was purified by column chromatography (P/MTBE = 98.5/1.5).…”

Recent developments in aromatic heteroatom coupling reactions

“…35 It has also been reported that S-allyl thiocarbonates 65 serve as convenient allylsulfenylation agents in the coupling of various aryl halides under typical Heck conditions (Scheme 17). 36 This is a very practical method that enables the preparation of allyl aryl sulfides without having to use allylthiostannanes or allyl thiols, both reagents being notorious for their stench, instability and toxicity. Another convenient method for the palladium catalysed preparation of mixed aryl sulfides 67 employs samarium() thiolates generated in situ from aryl thiocyanates 66 (Scheme 18).…”