SOCl2- and POCl3-activated β-chloroselenenation of alkenes

Зык, Н. В.; Белоглазкина, Е. К.; Antipin, R. L.

doi:10.1007/s11172-005-0132-8

Cited by 6 publications

(5 citation statements)

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“…In the literature, the efficient trans-addition of PhSeCl to alkenes, such as cyclohexene, is reported. [13] Astonishingly, this addition process to the alkene seems to be "reversible" in the presence of other halide anions, such as iodide, so that PhSeI and Cl À are formed while the alkene is regenerated, as was reported by Goto (Scheme 3). [14] Therefore, iodide anions will lead to the reverse process and cannot be applied as low-redox potential mediator to oxidise the envisaged Se(II) intermediate 6 (Scheme 3) to a Se(IV) species 5.…”

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confidence: 72%

The Electrochemical cis‐Chlorination of Alkenes

Strehl

Fastie

Hilt

2021

Chemistry A European J

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The first example for the electrochemical cisdichlorination of alkenes is presented. The reaction can be performed with little experimental effort by using phenylselenyl chloride as catalyst and tetrabutylammoniumchloride as supporting electrolyte, which also acts as nucleophilic reagent for the S N 2-type replacement of selenium versus chloride. Cyclic voltammetric measurements and control experiments revealed a dual role of phenylselenyl chloride in the reaction. Based on these results a reaction mechanism was postulated, where the key step of the process is the activation of a phenylselenyl chloride-alkene adduct by electrochemically generated phenylselenyl trichloride. Like this, different aliphatic and aromatic cyclic and acyclic alkenes were converted to the dichlorinated products. Thereby, throughout high diastereoselectivities were achieved for the cis-chlorinated compounds of > 95 : 5 or higher.

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confidence: 72%

The Electrochemical cis‐Chlorination of Alkenes

Strehl

Fastie

Hilt

2021

Chemistry A European J

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“…IR, ν/cm -1 : 3375, 3360 (NH 2 ). 1 This work was financially supported by the Russian Foundation for Basic Research (Project No. 08 03 00707a) and Presidium of the Russian Academy of Sci…”

Section: Methodsmentioning

confidence: 99%

“…1 H and 13 C NMR spectra were recorded on a Varian VXR 400 instrument in CDCl 3 at 400.13 and 100.61 MHz, respectively. IR spectra were obtained on a UR 20 instrument for suspensions in Nujol.…”

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β-Aminoselenenation of alkenes with arylselenenamides in the presence of sulfamic acid

et al. 2011

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In the present study, we suggested a new method of the synthesis of β aminoalkyl aryl selenides by the reaction of electrophilic selenenation of alkenes with phenylselen enamide 1 in the presence of HOSO 2 NH 2 .We have shown earlier that the reaction of arylselenen amides with unsaturated compounds in the presence of phosphorus(V) or sulfur(IV) oxohalides results in the cor responding β halogenalkyl aryl selenides in high yields. 1,2 Also, the possibility of a reaction of arylsulfenamides with olefins in the presence of sulfamic acid resulting in substi tuted aminoalkyl aryl sulfides was found. 3It is of note that the Gabriel reaction of nucleophilic substitution of the amino group for halogen successfully used for the preparation of β aminoalkyl sulfides 4 is inap plicable in the case of selenium containing analogs. The other known method for obtaining β aminoalkyl aryl se lenides (in the form of NBoc derivatives) 5 with olefins as the starting compounds requires preliminary aziridination of the alkenes, the use of indium iodide, and the inert atmosphere.We used cyclohexene and hex 1 ene in our experi ments. The reaction of phenylselenenamide 1 (see Ref.3) with hex 1 ene occurs regioselectively with the formation of 2 amino 1 phenylselenohexane (2). trans Amino se lenide 3 was obtained from cyclohexene (Scheme 1).The structures of the obtained products were estab lished by 1 H and 13 C NMR spectroscopy. In the 1 H NMR spectrum of amino selenide 2, a half width of the signals for the protons HCSe and HCN is ∼25 Hz, which unam biguously indicated trans diequatorial orientation of the substituents and the axial positions of the corresponding protons of the cyclohexane moiety. In the two dimen sional correlation spectrum 13 C-1 H HMBC of compound 3, intense cross peaks corresponding to the C(1´)-H a (1) and C(1´)-H b (1) ( 3 J) couplings are present. Besides, in the 13 C NMR spectrum of amino selenide 3 satellite peaks were observed corresponding to the 77 Se and 13 C coupling with J = 65 Hz.Thus, we suggested a convenient method for the syn thesis of primary alkylamines containing arylseleno group in the β position.

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“…3 The sulfenylation and selenenation of norbornene with the electron withdrawing CF 3 group gave no Wagner-Meerwein rearrangement products either. Simi larly, the corresponding trans 1,2 chloroselenides have been isolated upon the selenenation of alkenes with selenenamides activated with sulfur(IV) and phosphorus(V) oxychlorides.…”

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“…Previously, we dem onstrated the possibility of chloro and bromosulfenylation of alkenes with arylsulfenamides in the presence of phos phorus oxyhalides, 1,2 chloroselenenation with arylselenen amides activated by sulfur(IV) and phosphorus(V) oxy chlorides, 3 and iodination of the C=C bonds on treat ment with potassium dichloroiodate(I). Previously, we dem onstrated the possibility of chloro and bromosulfenylation of alkenes with arylsulfenamides in the presence of phos phorus oxyhalides, 1,2 chloroselenenation with arylselenen amides activated by sulfur(IV) and phosphorus(V) oxy chlorides, 3 and iodination of the C=C bonds on treat ment with potassium dichloroiodate(I).…”

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confidence: 99%

Electrophilic addition to norbornene derivatives containing CF3 and NO2 groups

et al. 2005

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Electrophilic sulfenylation, selenenation, and halogenation of bicyclo[2.2.1]heptenes con taining CF 3 or NO 2 group in position endo 5 were studied. The sulfenylation and selenenation were accomplished by arylsulfene and arylselenenamides activated by POHal 3 (Hal = Br, Cl), and iodination was performed by KICl 2 . The reactions are regiospecific and involve an exo attack of the electrophilic fragment (arylthio or arylseleno group or iodine) on the C=C bond atom located closer to the CF 3 or NO 2 group.

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SOCl2- and POCl3-activated β-chloroselenenation of alkenes

Cited by 6 publications

References 1 publication

The Electrochemical cis‐Chlorination of Alkenes

The Electrochemical cis‐Chlorination of Alkenes

β-Aminoselenenation of alkenes with arylselenenamides in the presence of sulfamic acid

Electrophilic addition to norbornene derivatives containing CF3 and NO2 groups

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