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Васин, В. А.; Kostryukov, S. G.; Razin, V. V.

doi:10.1023/a:1022597614806

Cited by 7 publications

(9 citation statements)

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“…The similar structure of the trimethylene bridge was also observed in the known 6,6,7-trisubstituted norpinanes of the endo,syn-configuration [2,4]. Our estimation performed using the calculation program RICON (method ZP) [5] suggested that both sixmembered rings C 6 C 1 C 2 C 3 C 4 C 5 and C 7 C 1 C 2 C 3 C 4 C 5 were in the envelop conformation with the folding parameters S 1.099, 1.072, θ 36.44, 38.49, ψ 2 0.23, 0.86…”

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confidence: 74%

“…The reaction in the dark of compound II with benzenesulfonyl bromide and also with Se-phenylbenzenesulfonoselenoate resulted in another order and another stereochemistry of the reagent addition to the C 1 -C 7 bond: we obtained norpinane compounds Va and Ve [2].…”

mentioning

confidence: 91%

“…Scheme 1. X SO 2 Ph SMe Va, Ve PhSO 2 X SR IIIa _ IIIc, IVb, IVd SR I, II PhSO 2 X PhSO 2 X, hvIt was shown formerly [1, 2] that 1-phenylthio-and 1-methylthiotricyclo[4.1.0.0 2,7 ]heptanes (I) and (II) under UV irradiation were subject to addition of benzenesulfonyl bromide, benzenesulfonyl chloride, S-phenylbenzenesulfonothioate, and S-methylbenzenesulfonothioate exclusively at the central bicyclobutane C 1 -C 7 bond strictly regio-and stereoselectively with the formation of norpinane compounds IIIa-IIIc and IVb, IVd.The reaction in the dark of compound II with benzenesulfonyl bromide and also with Se-phenylbenzenesulfonoselenoate resulted in another order and another stereochemistry of the reagent addition to the C 1 -C 7 bond: we obtained norpinane compounds Va and Ve [2].The difference in the behavior of the methylthioether II with respect to benzenesulfonyl halides was ascribed to the change in the addition mechanism from the radical at UV irradiation (benzenesulfonyl chloride) to the ionic one in the dark (benzenesulfonyl bromide). The successful reaction in the dark in this case is apparently favored by lower strength and larger polarity of the SO 2 -Br bond compared with the SO 2 -Cl bond and also by higher nucleophilicity of compound II than compound I.…”

mentioning

confidence: 92%

“…It was shown formerly [1,2] that 1-phenylthio-and 1-methylthiotricyclo[4.1.0.0 2,7 ]heptanes (I) and (II) under UV irradiation were subject to addition of benzenesulfonyl bromide, benzenesulfonyl chloride, S-phenylbenzenesulfonothioate, and S-methylbenzenesulfonothioate exclusively at the central bicyclobutane C 1 -C 7 bond strictly regio-and stereoselectively with the formation of norpinane compounds IIIa-IIIc and IVb, IVd.…”

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confidence: 99%

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Regio- and stereoselective addition of methane- and bromomethanesulfonyl bromides to 1-phenylthiotricyclo[4.1.0.02,7]heptane

et al. 2010

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1-Phenylthiotricyclo[4.1.0.0 2,7 ]heptane reacted with MeSO 2 Br and BrCH 2 SO 2 Br directly at mixing at 20°C in CH 2 Cl 2 along a ionic (electrophilic with respect to bromine) mechanism affording a product of an antistereoselective addition to the central bicyclobutane C 1 -C 7 bond of the norpinane structure. The reaction product contains the exo-oriented sulfonyl group in the geminal position to the SPh substituent. The structure of the adduct with MeSO 2 Br in a single crystal was determined by XRD analysis. Scheme 1. X SO 2 Ph SMe Va, Ve PhSO 2 X SR IIIa _ IIIc, IVb, IVd SR I, II PhSO 2 X PhSO 2 X, hvIt was shown formerly [1, 2] that 1-phenylthio-and 1-methylthiotricyclo[4.1.0.0 2,7 ]heptanes (I) and (II) under UV irradiation were subject to addition of benzenesulfonyl bromide, benzenesulfonyl chloride, S-phenylbenzenesulfonothioate, and S-methylbenzenesulfonothioate exclusively at the central bicyclobutane C 1 -C 7 bond strictly regio-and stereoselectively with the formation of norpinane compounds IIIa-IIIc and IVb, IVd.The reaction in the dark of compound II with benzenesulfonyl bromide and also with Se-phenylbenzenesulfonoselenoate resulted in another order and another stereochemistry of the reagent addition to the C 1 -C 7 bond: we obtained norpinane compounds Va and Ve [2].The difference in the behavior of the methylthioether II with respect to benzenesulfonyl halides was ascribed to the change in the addition mechanism from the radical at UV irradiation (benzenesulfonyl chloride) to the ionic one in the dark (benzenesulfonyl bromide). The successful reaction in the dark in this case is apparently favored by lower strength and larger polarity of the SO 2 -Br bond compared with the SO 2 -Cl bond and also by higher nucleophilicity of compound II than compound I.We investigated in this study the reactions of phenylthioether I with more active than PhSO 2 Br sources of electrophilic bromine, methane-and bromomethanesulfonyl bromides, aiming at establishing the regio-and stereoselectivity of these reagents addition. The reaction was carried out at 0°C in CH 2 Cl 2 over 6-8 h using equimolar amounts of the reagents; the reaction did not require a special initiation. By column chromatography on Al 2 O 3 we isolated from the reaction mixtures norpinane compounds VI and VII analogous to compounds Va R = Ph (I, III), Me (II, IV); X = Br (a), Cl (b), SPh (c), SMe (d), SePh (e).

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confidence: 74%

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confidence: 91%

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confidence: 92%

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confidence: 99%

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Regio- and stereoselective addition of methane- and bromomethanesulfonyl bromides to 1-phenylthiotricyclo[4.1.0.02,7]heptane

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“…Nonempirical calculations were performed by the restricted Hartree-Fock method in the basis 6-31G (for iodine atom into the standard basis were included the functions from the basis STO-6G) at preliminary parametrization by PM3 method using the program PC GAMESS 7.1 [14]. Tricycloheptane III was obtained as described in [16].…”

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Regio- and stereoselectivity in halomethoxylation of 7-phenyl-1-phenylsulfonyltricyclo[4.1.0.02,7]heptane

et al. 2010

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The reaction of 7-phenyl-1-phenylsulfonyltricyclo[4.1.0.0 2,7 ]heptane with N-halo (chloro, bromo, iodo)succinimide in methanol led to the formation of a single product of conjugate syn-addition to the central C 1 -C 7 bond of the norpinane structure with a halogen atom in the geminal position to the sulfonyl substituent. The stereochemical result of the addition originates from the features of the reaction intermediate structure, a norpinanyl cation of a benzyl type where the reaction site is shielded from the nucleophile attack from the anti-direction by the sulfonyl group whose oxygen atom is approached to the reaction site to a distance of ~1.45 according to the nonempirical calculations by the 6-31G method; this distance is nearly by half less than the sum of van der Waals radii of C···O.It was established experimentally that 1-phenyltricyclo[4.1.0.0 2,7 ]heptane (I) and its 7-X-substituted derivatives II-V were involved into the electrophilic addition: hydromethoxylation[1, 2], hydration [2, 3], ionic hydrogenation [4], methoxymercuration [1], halogenation [3], halomethoxylation [1, 3, 5, 6], haloamination [6], and other reactions of conjugate halogenation [3,7] and exhibited strict chemo-and regioselectivity. In these reactions the C 1 -C 7 bond opened at an electrophilic attack on the position 7, as a result of the benzyl stabilization of intermediate norpinanyl cation A [8,9]. From this rule in this series only the hydration and the hydromethoxylation of tricycloheptane I are excluded, where the chemoselectivity of the addition is broken: alongside the norpinane adduct (4 and 18% respectively) formed predominantly a norcarane adduct (54 and 56%) corresponding to the opening of the C 2 -C 7 bond also at the electrophilic attack on the position 7 [2]. As to the stereochemistry of the addition to the C 1 -C 7 bond, here its certain dependence is observed on the nature of the reagent and the character of the substituent X in the position 7. Yet this dependence corresponds only to the stage of the transfer of the nucleophilic coreagent to carbocation A, since the stage of the electrophilic attack on the central bicyclobutane bond C 1 -C 7 is considered to be strictly endo-directed [8,9]. As a result the X = H (I), CO 2 Me (II), SO 2 Ph (III), Br (IV), Cl (V); E = H, Cl, Br, I, HgOAc; Nu = H, OH, OMe, OCOR, Cl, Br, I, NHCN, SCN, N(COCH 2 ) 2 X Ph X E Ph Nu X E Ph Nu anti-adduct Nu + E + syn-adduct I _ V A X E Ph _

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Products of Reaction of Tricyclo[4.1.0.0^2,7]heptane and 1‐Bromotricyclo[4.1.0.0^2,7]heptane with Hydrogen Sulfide, and Syntheses Based Thereon.

2003

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Bridged compoundsBridged compounds Q 0060 Products of Reaction of Tricyclo[4.1.0.0 2,7 ]heptane and 1-Bromotricyclo[4.1.0.0 2,7 ]heptane with Hydrogen Sulfide, and Syntheses Based Thereon. -UV-irradiation of title tricycloheptane derivatives like (I) in the presence of hydrogen sulfide furnishes the corresponding thiols [cf. (II)] and sulfides [cf. (III)] with regioselective opening of the central C(1)-C(7) bond. In the presence of bromine substituent, the reaction proceeds with excellent stereoselectivity. Oxidation of the sulfide can be carried out selectively to give sulfoxides [cf. (IV)] or sulfones [cf. (VI)] in good yields. Dehydrobromination of these sulfoxides and sulfones provides access to the sulfoxides and sulfones of the tricycloheptane series. It is shown, however, that only bromine substituents in syn-position can be eliminated [cf. (VIII) vs. (IX)]. -(VASIN, V. A.; KOSTRYKOV, S. G.; RAZIN, V. V.; Russ. J. Org. Chem. 38 (2002) 11, 1582-1587; Ogarev Mordovian State Univ., Saransk 430000, Russia; Eng.) -Mischke 25-099 2003 Bridged compounds

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Untitled

Cited by 7 publications

References 3 publications

Regio- and stereoselective addition of methane- and bromomethanesulfonyl bromides to 1-phenylthiotricyclo[4.1.0.02,7]heptane

Regio- and stereoselective addition of methane- and bromomethanesulfonyl bromides to 1-phenylthiotricyclo[4.1.0.02,7]heptane

Regio- and stereoselectivity in halomethoxylation of 7-phenyl-1-phenylsulfonyltricyclo[4.1.0.02,7]heptane

Products of Reaction of Tricyclo[4.1.0.0^2,7]heptane and 1‐Bromotricyclo[4.1.0.0^2,7]heptane with Hydrogen Sulfide, and Syntheses Based Thereon.

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Untitled

Cited by 7 publications

References 3 publications

Regio- and stereoselective addition of methane- and bromomethanesulfonyl bromides to 1-phenylthiotricyclo[4.1.0.02,7]heptane

Regio- and stereoselective addition of methane- and bromomethanesulfonyl bromides to 1-phenylthiotricyclo[4.1.0.02,7]heptane

Regio- and stereoselectivity in halomethoxylation of 7-phenyl-1-phenylsulfonyltricyclo[4.1.0.02,7]heptane

Products of Reaction of Tricyclo[4.1.0.02,7]heptane and 1‐Bromotricyclo[4.1.0.02,7]heptane with Hydrogen Sulfide, and Syntheses Based Thereon.

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Products of Reaction of Tricyclo[4.1.0.0^2,7]heptane and 1‐Bromotricyclo[4.1.0.0^2,7]heptane with Hydrogen Sulfide, and Syntheses Based Thereon.