Catalytic Thia-Sommelet−Hauser Rearrangement: Application to the Synthesis of Oxindoles

Abstract

A series of 3-arylthio-1,3-disubstituted-oxindoles were prepared in good yields by the reaction of α-diazocarbonyl compounds and sulfenamides. The reaction involves a Rh-catalyzed thia-Sommelet-Hauser-type rearrangement.

Recent Advances in the Base‐Induced Sommelet–Hauser Rearrangement of Amino Acid Derived Ammonium Ylides

“…Next, the fluoride‐induced S–H rearrangement was developed and studied by Sato and Shirai's group in 1985–1999. Later, further reports on this rearrangement were quite limited . In 2007, my co‐workers and I successfully demonstrated that the asymmetric rearrangements of N ‐benzylic ammonium ylides using a chiral auxiliary undergo exclusively the S–H rearrangement.…”

Rhodium(ii)-catalyzed direct sulfenylation of diazooxindoles with disulfides

“…1 H NMR and 13 C NMR spectra were recorded on a Varian VNS or DPX (600 or 300 and 150 or 75 MHz, respectively) spectrometer in CDCl 3 , DMSO-d 6 , or acetone-d 6 using d ¼ 7.24 and 77.00 ppm or 2.5 and 39.5 ppm or 2.05 and 29.8 ppm as the internal standard solvent chemical shis, respectively. 20 All other reagents and solvents were purchased at the highest commercial quality and used without further purication.…”

“…[5][6][7][8][9] Representative approaches include Gassman synthesis via a thia-Sommelet-Hauser rearrangement from anilines as the key step (path a, Scheme 1) 5 and a reaction of diazocarbonyl compounds with aniline derivatives followed by thia-Sommelet-Hauser rearrangement (path b, Scheme 1). 1 Among these, oxindoles bearing heteroatoms as substituents at the C3 position are particularly important and useful in medicinal chemistry.…”

Organocatalytic, Asymmetric Synthesis of 3‐Sulfenylated N‐Boc‐Protected Oxindoles

“…Recently, Wang, Zhang et al. developed a Rh(OAc) 2 ‐catalyzed thia‐Sommelet–Hauser rearrangement that led to the formation of 3‐arylthiooxindoles in moderate to good yields 8h. However, the direct, asymmetric construction of oxindoles that have a sulfur‐containing tetrasubstituted stereocenter remains elusive.…”