Hypervalent Iodine-Induced Multi-Component Reactions: Novel Thiocyano- and Isothiocyano-phenylselenenylating Reaction of Alkenes

Abstract

A simple and efficient thiocyano‐ or isothiocyano‐phenylselenenylation of alkenes has been developed. The reactions occur when alkenes are treated with [bis(acetoxy)iodo]benzene, trimethylsilyl isothiocyanate or potassium thiocyanate and diphenyl diselenide. Mono‐ and disubstituted alkenes led to the formation of 1,2‐phenylseleno‐thiocyanates, whereas both more‐substituted alkenes and styrenes gave exclusively 1,2‐phenylseleno‐isothiocyanates. The overall transformation represents the addition of PhSeSCN to the olefinic double bonds, in situ generated by the above reagents combination.

Advances in Synthetic Applications of Hypervalent Iodine Compounds

“…594 Reactions of cyclohexene and 1methylcyclohexene under these conditions proceed stereoselectively affording the respective trans-adducts. 594,595 The arylselenation reaction of various alkenes by diaryl diselenides in the presence of (diacetoxyiodo)benzene has been reported by Tingoli and co-workers. 597−600 The phenylselenated products are obtained in good yields from the corresponding alkenes, diphenyl diselenide, and DIB in acetonitrile.…”

Advances in Synthetic Applications of Hypervalent Iodine Compounds

“…594 Reactions of cyclohexene and 1methylcyclohexene under these conditions proceed stereoselectively affording the respective trans-adducts. 594,595 The arylselenation reaction of various alkenes by diaryl diselenides in the presence of (diacetoxyiodo)benzene has been reported by Tingoli and co-workers. 597−600 The phenylselenated products are obtained in good yields from the corresponding alkenes, diphenyl diselenide, and DIB in acetonitrile.…”

Advances in Difunctionalization of Olefins with Diorganyl Dichalcogenides

“…In 2000, Piancatelli and colleagues reported the selenylation of alkenes with bis(acetoxy)iodobenzene (BAIB) and trimethylsilyl isothiocyanate (TMSNCS) (Scheme 21). [39] It was observed that the reaction is not chemically selective, meaning that different substrates result in the formation of different products.…”

Synthesis of a Series of Promising Isobenzofuranones for the Treatment of Acute Mucositis Caused by Chemo- and Radiotherapy

“…These three intermediates were then subjected to a solution of refluxing acetic anhydride to yield the corresponding anhydrides 11a-c. Gratifyingly, addition of the Gilman cadmium reagent, formed after addition of one equivalent of anhydrous cadmium chloride to a cold solution of two equivalents of methylmagnesium bromide 12,13 furnished the desired products 1, 2 and 3 in moderate to good yields (Scheme 2, Table 1). 14 For the preparation of compound 4, we adapted a protocol from Piancatelli et al 15 where a hypervalent iodine(III) reagent, [bis(acetoxy)iodo]benzene (BAIB or PhI(OAc) 2 ], was involved in a multicomponent reaction to facilitate the formation of the desired allylic alcohol. As predicted, the necessary tertiary alcohol motif was attained by oxidative removal of the phenylselenium group with aqueous sodium periodate in 1,4-dioxane (Scheme 4).…”

Advances in Synthetic Applications of Hypervalent Iodine Compounds

“…594 Reactions of cyclohexene and 1methylcyclohexene under these conditions proceed stereoselectively affording the respective trans-adducts. 594,595 The arylselenation reaction of various alkenes by diaryl diselenides in the presence of (diacetoxyiodo)benzene has been reported by Tingoli and co-workers. 597−600 The phenylselenated products are obtained in good yields from the corresponding alkenes, diphenyl diselenide, and DIB in acetonitrile.…”

Advances in Difunctionalization of Olefins with Diorganyl Dichalcogenides

“…In 2000, Piancatelli and colleagues reported the selenylation of alkenes with bis(acetoxy)iodobenzene (BAIB) and trimethylsilyl isothiocyanate (TMSNCS) (Scheme 21). [39] It was observed that the reaction is not chemically selective, meaning that different substrates result in the formation of different products.…”

Synthesis of a Series of Promising Isobenzofuranones for the Treatment of Acute Mucositis Caused by Chemo- and Radiotherapy

“…These three intermediates were then subjected to a solution of refluxing acetic anhydride to yield the corresponding anhydrides 11a-c. Gratifyingly, addition of the Gilman cadmium reagent, formed after addition of one equivalent of anhydrous cadmium chloride to a cold solution of two equivalents of methylmagnesium bromide 12,13 furnished the desired products 1, 2 and 3 in moderate to good yields (Scheme 2, Table 1). 14 For the preparation of compound 4, we adapted a protocol from Piancatelli et al 15 where a hypervalent iodine(III) reagent, [bis(acetoxy)iodo]benzene (BAIB or PhI(OAc) 2 ], was involved in a multicomponent reaction to facilitate the formation of the desired allylic alcohol. As predicted, the necessary tertiary alcohol motif was attained by oxidative removal of the phenylselenium group with aqueous sodium periodate in 1,4-dioxane (Scheme 4).…”

Advances in Synthetic Applications of Hypervalent Iodine Compounds

“…594 Reactions of cyclohexene and 1methylcyclohexene under these conditions proceed stereoselectively affording the respective trans-adducts. 594,595 The arylselenation reaction of various alkenes by diaryl diselenides in the presence of (diacetoxyiodo)benzene has been reported by Tingoli and co-workers. 597−600 The phenylselenated products are obtained in good yields from the corresponding alkenes, diphenyl diselenide, and DIB in acetonitrile.…”

Advances in Difunctionalization of Olefins with Diorganyl Dichalcogenides

“…In 2000, Piancatelli and colleagues reported the selenylation of alkenes with bis(acetoxy)iodobenzene (BAIB) and trimethylsilyl isothiocyanate (TMSNCS) (Scheme 21). [39] It was observed that the reaction is not chemically selective, meaning that different substrates result in the formation of different products.…”

Synthesis of a Series of Promising Isobenzofuranones for the Treatment of Acute Mucositis Caused by Chemo- and Radiotherapy

“…These three intermediates were then subjected to a solution of refluxing acetic anhydride to yield the corresponding anhydrides 11a-c. Gratifyingly, addition of the Gilman cadmium reagent, formed after addition of one equivalent of anhydrous cadmium chloride to a cold solution of two equivalents of methylmagnesium bromide 12,13 furnished the desired products 1, 2 and 3 in moderate to good yields (Scheme 2, Table 1). 14 For the preparation of compound 4, we adapted a protocol from Piancatelli et al 15 where a hypervalent iodine(III) reagent, [bis(acetoxy)iodo]benzene (BAIB or PhI(OAc) 2 ], was involved in a multicomponent reaction to facilitate the formation of the desired allylic alcohol. As predicted, the necessary tertiary alcohol motif was attained by oxidative removal of the phenylselenium group with aqueous sodium periodate in 1,4-dioxane (Scheme 4).…”