in situ Formation of RSCl/ArSeCl and Their Oxidative Coupling with Enaminone Derivatives Under Transition‐metal Free Conditions

Abstract

The reaction of diorganyl disulfides or diselenides with PhICl 2 in DMF at room temperature led to the in situ formation of the reactive organosulfenyl chloride (RSCl) or selenenyl chloride (ArSeCl), which reacted with enaminone compounds to afford a series of α-thioenaminones or α-selenylenaminones, respectively, including the bioactive inhibitor for Cdc25B and its analogue, via the intermolecular oxidative C(sp 2 )-S/Se cross coupling reactions under metal-free conditions.

Insights into the Recent Synthetic Advances of Organoselenium Compounds

“…[92] Yunfei et. al., [93] achieved novel metal-free α-selenylation of enamines 35 through C(sp 2 )-Se bond formation (Scheme 16). The reactive electrophile PhSeCl was generated in situ (mechanism shown in scheme 4) as a product of reaction between diselenides and PhICl 2 .…”

Research Progress in C—S Bond Formation Reaction of Olefins with Organic Sulfur Reagents under Photocatalyst-Free and Non-Electrochemical Conditions

“…纪顺俊课题组 [58] 其他类型的 α,β-不饱和羰基化合物(如 α,β-不饱和酰 胺)与二硫醚反应, 在 C＝C 键上构建 C-S 键同样引起 了科学家的兴趣 [59][60][61] . 纪顺俊课题组 [62] 开发了铑、铜共 催化二硫醚在 α,β-不饱和酰胺的 β-位构建 C-S 键反应, 产率中等至较高(Eq.…”

Intramolecular Chalcogenylation of Isooxazolines Mediated by PhICl2 and Diorganyl Disulfides or Diselenides

“…Paper Synthesis 13 C NMR (101 MHz, CDCl 3 ):  = 156. 7, 143.5, 134.1, 133.0, 133.0, 130.7, 129.2, 128.6, 128.5, 128.4, 127.9, 127.9, 127.2, 127.2, 127.1, 127.0, 126.7, 125.3, 123.5, 90.5, 46.0, 39. 7.49 (dd, J = 8.3, 1.1 Hz, 2 H), 7.46-7.42 (m, 2 H), 7.37 (t, J = 7.7 Hz, 2 H), 7.30 (t, J = 7.9 Hz, 1 H), 7.24-7.17 (m, 3 H), 3.85 (d, J = 16.5 Hz, 1 H), 3.67-3.41 (m, 3 H). 13…”

“…To test our hypothesis on the sulfenylation of ,-unsaturated oximes by the organosulfenyl chloride generated in situ, substrate 1a was initially employed as model substrate to react with PhSSPh and PhICl 2 under various conditions (Table 1). To our delight, subjecting a solution resulting from the reaction of PhSSPh (0.5 equiv) and PhICl 2 (0.7 equiv) 6,7 to ,-unsaturated oxime 1a (1.0 equiv) delivered the desired sulfenylated isooxazoline 2a in a yield of 85%. Increasing the amount of PhICl 2 from 0.7 to 1.0 equiv resulted in decreased yield (entries 1-4).…”