The Synthesis of <i>Se</i>-Alkyl Alkaneselenoates via (1-Iodo-1-alkenyl)dialkylboranes

Hoshi, Masayuki; Masuda, Yoshio; Arase, Akira

doi:10.1246/bcsj.61.3764

Cited by 20 publications

(12 citation statements)

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“…A particularly cheap, simple and straightforward method for the preparation of metal selenolates is the reaction of Grignard reagents RMgX with elemental selenium, pioneered more than a century ago by French scientists, affording selenolates of the type RSeMgX . Although this reaction has been studied predominantly for aryl derivatives, aliphatic compounds of this type are easily accessible, too . Note that in the present context the use of such sselenolates prepared in situ from a Grignard reagent and elemental selenium avoids the hazards associated with highly toxic selenols …”

Section: Resultsmentioning

confidence: 99%

Phthalocyanine Derivatives with Eight Peripheral Long‐Chain n‐Alkylseleno Substituents

et al. 2016

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4,5-Bis(n-octylseleno)phthalodinitrile and 4,5-bis(ndodecylseleno)phthalodinitrile were efficiently synthesised from 4,5-dichlorophthalodinitrile and the corresponding selenolate RSeMgBr (prepared in situ from elemental selenium and RMgBr; R = n-octyl, n-dodecyl). Lithium chloride was essential for achieving the substitution of both chloro substituents. The crystal structures of the monosubstitution product 4-chloro-5n-octylselenophthalodinitrile and both disubstitution products were determined by single-crystal X-ray diffraction, with that of 4,5-bis(n-dodecylseleno)phthalodinitrile exhibiting inter- [a] 5610 molecular C-H···Se contacts compatible with hydrogen bonds. Cyclotetramerisation of these 4,5-bis(n-alkylseleno)phthalodinitriles under Tomoda conditions afforded the corresponding 2,3,9,10,16,17,23,24-octakis(n-alkylseleno)phthalocyanines Pc SeR H 2 (R = n-octyl, n-dodecyl). The phthalocyaninatomanganese(III) complexes [MnCl(Pc SeR )] were obtained from the cyclotetramerisation in the presence of manganese(II) chloride after aerobic workup. The use of terbium(III) chloride as metal salt in the cyclotetramerisation furnished the "double-decker" complexes [Tb(Pc SeR ) 2 ].

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Section: Resultsmentioning

confidence: 99%

Phthalocyanine Derivatives with Eight Peripheral Long‐Chain n‐Alkylseleno Substituents

et al. 2016

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“…4-Methyl-3-(phenylseleno-rnethy1ene)-1 -benzenesulfonylpyrrolidine 10b (0.17 g, 42%) was obtained as white prisms (dichloromethane-hexane), m.p. 75-77 "C; v,,,/cm-' 1350 and 1160 (SO,); 6,(270 MHz; CDC1,) 1.07 (3 H,d,J 6,m,m,3.76(1 H,brd,J15,3.94(1 H,dd,J15and 1,6.24 (1 H,br s,m,ArH) (Found: C, 54.8; H, 5.0 N, 3.5. C *H ,NO,SSe requires C, 55.1; H, 4.9; N, 3.6%).…”

Section: N-butyn-3-yl-n-(3-methylbut-2-enyl)toluene-p-sulfonamidementioning

confidence: 99%

“…The title compound 9a (1.42 g, 62%) was obtained as white prisms, m.p. 80-81 "C; vmax/cm-l 3250 ( H W ) and 2100 s, Me), 3.99 (2 H, d, J 6, CH,C=), 4.12 (2 H, d, J 2, CH,C=C), 6.07 (1 H, dt, J 6 and 16, CH2CH=), 6.57 (1 H,d,J 16,=CHPh),m,ArH)…”

Section: N-cinnamyl-n-prop-2-ynyltoluene-p-sulfonamide 9a-a Dmf (8 Cm...mentioning

confidence: 99%

“…Reaction of 2b with Phenylacety1ene.-The reaction of 2b (0.49 g, 1.0 mmol) and phenylacetylene (0.18 g, 1.8 mmol) in CH,Cl, (3 cm3) afforded (Z)-P-phenylselenostyrene 3f (0.37 g, 79%) as a yellow oil and (E)-a$-bis(phenylse1eno)styrene 4f (0.09 g, 12%) as a yellow oil. 3f: 6,(60 MHz; CDC1,) 6.68 (1 H, d, J 10, olefinic H), 6.91 (1 H, d, J 10, olefinic H) Reaction of 2b with Dodecyne.-The reaction of 2b (0.54 g, 1.1 mmol) and dodecyne (0.39 g, 2.0 mmol) afforded a mixture of (E)-and (Z)-1-phenylselenododec-1-ene 3g (0.57 g, 72%) as a yellow oil; vmax/cm-l 285&2950 (alkyl); 6,(270 MHz; CDCl,) 0.85-0.90 [3 H, m, ( E ) -and (2)-Me], m,CH,), 2.1 1-2.19 (2 H, m, CH,), 6.00-6.43 (4 H, m, olefinic H) and 7.20-7.52 (5 H, m, ArH) (Found: M + , 352.1686. C,,H,,Se requires M , 352.1669).…”

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confidence: 99%

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Versatile cyclisation reactions using selenoboranes

Kataoka¹,

Yoshimatsu²,

Noda³

et al. 1993

J. Chem. Soc., Perkin Trans. 1

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Tris( phenylseleno) borane and tris(methylse1eno) borane reacted with terminal acetylenes to afford (Z)vinyl selenides. This reaction was initiated by oxygen and the intermediates were vinyl radicals. This radical reaction could be applied t o the intramolecular free radical cyclisation of enynes and some heterocycles and carbocycles were synthesised. This novel method could be also employed in the synthesis of a-kainoid derivatives.Selenyl radicals are reactive chemical species and their addition to multiple bonds is synthetically useful.' The phenylselenyl radical can be readily generated by photolysis of diphenyl diselenide or by oxidation of benzeneselenol with oxygen, and adds to olefins,2 acetylenes or a l l e n e ~. ~ Photochemical and thermal reactions'' of Se-phenyl areneselenosulfonates cause the free radical selenosulfonation to multiple bonds.On the other hand, the intramolecular addition of carbon free radicals to carbon-carbon multiple bonds constructs the fiveand six-membered rings.6 In particular, the exo-methylene substituted five-membered rings are formed by the intramolecular capture of vinyl radicals with double bonds. The vinyl radicals are generated by addition of carbon-or heteroatomcentred radicals to acetylenes7 Oshima et al. found the facile radical additions of R,GeH,* RSH or R,SnH l o to acetylenes induced by triethylborane, and developed the method to the synthesis of five-membered rings with a R,Ge-, RS-or R,Snsubstituted methylene group. However, the triethylboraneinduced hydroselenation of acetylenes did not give satisfactory results.' ' It has been reported that consecutive reactions of iodoacetylenes with bis( 1,2-dimethylpropyl)borane and with alkylselenomagnesium bromide afforded vinyl selenides. 'Recently Hevesi reported that the organoselenoboranes which are generally utilised for selenoacetalisation of aldehydes or ketones,' added to a$-unsaturated ketones. l 4 These reports prompted us to examine the reactions of organoselenoboranes with acetylenes and we revealed that organoselenoboranes caused free radical 1,2-addition to acetylenes.'5 We have been interested in the phenylselenomethylene-substituted five-membered ring compounds, since these compounds can be employed in the synthesis of biologically active compounds by transformation of the phenylselenomethylene group to other groups.I6 This paper gives full details of the addition reactions of organoselenoboranes and their application to radical cyclisation of some enynes. Results and DiscussionSelenoborane reagents 2a and 2b were treated with acetylenes in dichloromethane at room temperature to afford mono-RSesubstituted ethylenes 3 and di-RSe-substituted ethylenes 4. The addition reactions occurred regio-and stereo-selectively at the terminal acetylenic carbon to form Z-vinyl selenides in satisfactory yields. However, reactions with an acetylenic alcohol provided low yields of vinyl selenides and reactions with disubstituted acetylenes gave no addition products."The mechanism of the addition reaction was investigated by...

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“…8 Selenol esters have been prepared by: (i) acylation or aroylation of selenols and their metal salts; 9 (ii) alkylation of selenocarboxylates; 10 (iii) reaction of carboxylic acids with selenocyanates or N-phenylselenophthalimide; 11 (iv) reaction of esters or aldehydes with aluminum selenolates; 4b,5a,6d,12 (v) transition-metal-catalysed carbonylation of diselenides; 13 (vi) reaction of carboxylic acids with diaryl diselenides; 14 and other miscellaneous methods. [15][16][17][18][19][20][21][22][23][24] These methods suffer from laborious removal of by-products such as diaryl diselenides, or in some cases, unavailability of reagents.…”

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confidence: 99%

Reductive Cleavage of the Se–Se Bond in the Presence of a Zn/AlCl₃ System: Synthesis of Selenol Esters

Movassagh

Shamsipoor

Joshaghani

2004

Journal of Chemical Research

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The Synthesis of Se-Alkyl Alkaneselenoates via (1-Iodo-1-alkenyl)dialkylboranes

Abstract: Se-Alkyl alkaneselenoates were formed in moderate to good yields by successive reactions of (1-iodo-1-alkenyl)bis(1,2-dimethylpropyl)boranes with alkylselenomagnesium bromides and alkaline hydrogen peroxide.

Cited by 20 publications

References 15 publications

Phthalocyanine Derivatives with Eight Peripheral Long‐Chain n‐Alkylseleno Substituents

Phthalocyanine Derivatives with Eight Peripheral Long‐Chain n‐Alkylseleno Substituents

Versatile cyclisation reactions using selenoboranes

Reductive Cleavage of the Se–Se Bond in the Presence of a Zn/AlCl₃ System: Synthesis of Selenol Esters

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The Synthesis of Se-Alkyl Alkaneselenoates via (1-Iodo-1-alkenyl)dialkylboranes

Abstract: Se-Alkyl alkaneselenoates were formed in moderate to good yields by successive reactions of (1-iodo-1-alkenyl)bis(1,2-dimethylpropyl)boranes with alkylselenomagnesium bromides and alkaline hydrogen peroxide.

Cited by 20 publications

References 15 publications

Phthalocyanine Derivatives with Eight Peripheral Long‐Chain n‐Alkylseleno Substituents

Phthalocyanine Derivatives with Eight Peripheral Long‐Chain n‐Alkylseleno Substituents

Versatile cyclisation reactions using selenoboranes

Reductive Cleavage of the Se–Se Bond in the Presence of a Zn/AlCl3 System: Synthesis of Selenol Esters

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Reductive Cleavage of the Se–Se Bond in the Presence of a Zn/AlCl₃ System: Synthesis of Selenol Esters