Darstellung von 1-substituierten tricyclo[4.1.0.02,7]heptanen

Szeimies, Günter; Philipp, F.; Baumgärtel, Otto; Harnisch, J.

doi:10.1016/s0040-4039(01)83700-x

Cited by 25 publications

(8 citation statements)

References 11 publications

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“…Ester 2 was discovered during our attempts to understand the unusual behavior of (CsHsjRejCOHNOXCHO). This neutral formyl complex is only moderately air sensitive and is relatively stable in solution under nitrogen, decomposing over several days to give (C5H5)Re(CO)(NO)(H) (4) as the pri-…”

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confidence: 99%

Intermediacy of tetracyclo[3.2.0.02.7.04.6]hept-1(7)-ene, a highly strained bridgehead olefin

Harnisch¹,

Baumgaertel²,

Szeimies³

et al. 1979

J. Am. Chem. Soc.

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Communications to the EditorOn the Intermediacy of Tetracyclo[3.2.0.02'7.04'6]hept-l(7)-ene, a Highly Strained Bridgehead Olefin Sir:Recently evidence has been accumulated that tricyclo[4.1.0.02'7]hept-l(7)-ene and related bicyclo[1.1.0]but-1 (3)-ene derivatives are formed as fleeting intermediates, when the corresponding bridgehead-halogen-substituted bicyclo[1.1.0]butanes are treated with a strong base.1 We now report our preliminary results on the quadricyclane2 system which indicate that the title compound might be a short-lived species, generated by the base treatment of 1-chloroquadricyclane (lc). Scheme I 1cThe synthesis of lc was achieved by metalating quadricyclane (la)3 with the «-butyllithium-tetramethylethylenediamine complex to lb (in «-hexane, 24 h at 20 °C) and chlorinating lb with /i-toluenesulfonyl chloride4 (yield 44%). Structure proof for lc rests on its 13C NMR spectrum ((CDC13) 14.04 (d), 23.65 (d), 24.92 (d), 26.97 (d), 31.23 (t), 31.73 (d), 45.77 (s)), its mass spectrum (m/e 126, 128 (M+)), and its facile conversion to 2-chloronorbornadiene,5 either thermally at 140 °C (in C(X>e, sealed NMR tube), or by catalysis with a trace of silver trifluoromethylsulfonate at 20 °C.

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confidence: 99%

Intermediacy of tetracyclo[3.2.0.02.7.04.6]hept-1(7)-ene, a highly strained bridgehead olefin

Harnisch¹,

Baumgaertel²,

Szeimies³

et al. 1979

J. Am. Chem. Soc.

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“…Substitution of hydrogen against bromine at C-6 of 11 and C-3 of 17 to afford 12 and 18 was achieved by metalation, for 11 with 2.2 equiv. of BuLi and occasionally of MeLi in ether, for 17 with BuLiRMEDA, followed by reaction with tosyl bromide [9]. As observed earlier [6], BuLi tends to lithiate the ortho position of aromatic rings fixed to the carbon atom which also carries the OH group.…”

Section: Bromination Of the Second Bicyclobutane Bridgehead Positionmentioning

confidence: 78%

Synthesis of [1.1.1]Propellanes by Cyclization of 3-Alkylidenecyclobutylidenes

1997

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Starting from tricyclo [3.1.0.02,6]hexane 5 and 1‐ bromobicyclo[1.1.0]butane 6, a series of [1.1.1]propellanes 15 and 21 has been synthesized which carry alkyl, aryl, alkenyl, and alkynyl groups. Propellane formation proceeded via 1‐bromo‐1‐chloro‐3‐alkylidenecyclobutanes of type 13 and 19, which on treatment with methyllithium gave rise to the generation of carbenes 14 and 20 as short‐lived intermediates. For these carbenes, the most efficient path of stabilization is obviously the intramolecular cycloaddition. Ab initio MO calculations at the Becke3LYP/6‐31G* and MP2/6‐31G* level of theory indicated that 3‐alkylidenecyclobutylidenes 4 and 37a–d are not local energy minima but collapse to the corresponding [1.1.1]propellanes. On this basis, propellane formation should follow a carbenoid reaction path.

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“…Tricycloheptane I [12], MeSO 2 Br [13], and BrCH 2 SO 2 Br [14] were obtained by published procedures.…”

Section: Methodsmentioning

confidence: 99%

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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Darstellung von 1-substituierten tricyclo[4.1.0.02,7]heptanen

Cited by 25 publications

References 11 publications

Intermediacy of tetracyclo[3.2.0.02.7.04.6]hept-1(7)-ene, a highly strained bridgehead olefin

Intermediacy of tetracyclo[3.2.0.02.7.04.6]hept-1(7)-ene, a highly strained bridgehead olefin

Synthesis of [1.1.1]Propellanes by Cyclization of 3-Alkylidenecyclobutylidenes

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

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