Halohydroxylation of alkylidenecyclopropanes using N-halosuccinimide (NXS) as the halogen source: an efficient synthesis of halocyclopropylmethanol and 3-halobut-3-en-1-ol derivatives

Photo-mediated selective deconstructive geminal dihalogenation of trisubstituted alkenes

“…Based on existing related literatures [43][44][45][46][47] and all the experimental results described above, a plausible mechanism was proposed and is described in Fig. 5d.…”

“…5d. The cascade reaction is initiated by hydroxyhalogenation of alkene I in the presence of water and an electrophilic halogen source 44 . The resulting halohydrin II reacts with DIH to deliver the alkyl hypoiodite intermediate III.…”

Construction of Carbocycles from Methylenecyclopropanes

“…As shown in Eq. (2), in 2009, Huang reported a solvent‐controlled selective hydrohalogenation reaction of MCPs . The reactions performed in aqueous acetone afforded CP‐retaining cyclopropylmethanols 9 in 31–95% yields [Eq.…”

Recent developments in the reactivity of methylene- and alkylidenecyclopropane derivatives

“…In order to enlarge this application and overcome some of its inherent limitations, such as inconvenience in use and environmental toxicity, these authors have explored the use of N-halosuccinimides (NXS) as more convenient, mild, and variable sources of electrophilic halogen. 35 As shown in Scheme 23, a variety of 3-halo-but-3-en-1-ol derivatives could be obtained in good-to-high yields by treating alkylidenecyclopropanes with various N-halosuccinimides as the halogen sources in aqueous DMSO at 100 C.…”

“…In order to enlarge this methodology and avoid the use of iodine, these authors have developed more general halohydroxylations of alkylidenecyclopropanes by using Nhalosuccinimides as the halogen source. 34,35 In this context, a wide range of 3-halobut-3-en-1-ol derivatives could be synthesised under mild conditions in moderate-to-excellent yields (31e93%). In a same area, Shi et al have shown that the reaction of arylmethylenecyclopropylcarbinols with iodine in the presence of K 2 CO 3 , or diphenyl diselenide in the presence of sulfuryl chloride, stereoselectively gave the corresponding ring-closure product, 1-iodo-2-aryl-3-oxabicyclo[3.1.0]hexane, or 1-phenylselenenyl-2-aryl-3-oxabicyclo[3.1.0]hexane, respectively, in good-to-high yields at room temperature (Scheme 114).…”