ChemInform Abstract: Functionalization of Tricyclo(4.1.0.02,7)heptanes by Phenylsulfonylbromination‐Dehydrobromination.

Васин, В. А.; Razin, V. V.; Kostryukov, S. G.; Bolusheva, I. Yu.; Зефиров, Н. С.

doi:10.1002/chin.199541126

ChemInform

1995

DOI: 10.1002/chin.199541126

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ChemInform Abstract: Functionalization of Tricyclo(4.1.0.02,7)heptanes by Phenylsulfonylbromination‐Dehydrobromination.

В. А. Васин

V. V. Razin

S. G. Kostryukov

et al.

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2010

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Cited by 4 publications

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“…The major products of acid-DOI: 10 catalyzed hydromethoxylation of 1-phenyltricycloheptane VI [6] were diastereoisomeric norcaranes VIIa and VIIb (56%); in addition, cycloheptene VIII (21%) and two norpinane diastereoisomers IXa and IXb (23%) were formed. Norpinane derivatives like IXa or IXb were not detected among hydromethoxylation products of tricycloheptanes I and III.…”

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Chemo-, regio-, and stereoselectivity in acid-catalyzed hydromethoxylation of tricyclo[4.1.0.02,7]hept-1-yl and 7-methyltricyclo[4.1.0.02,7]hept-1-yl phenyl sulfones

et al. 2010

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Hydromethoxylation of tricyclo[4.1.0.0 2,7 ]hept-1-yl and 7-methyltricyclo[4.1.0.0 2,7 ]hept-1-yl phenyl sulfones with methanol at 20°C in the presence of a catalytic amount of perchloric acid is initiated by the endo attack of proton at the C 1 atom, and the subsequent cleavage of the side C 1 -C 2 bond leads to formation of mixtures of diastereoisomeric exo-7-phenylsulfonyl-2-methoxybicyclo[4.1.0]heptanes, the endo-2 isomer prevailing. Probable factors responsible for the observed chemo-, regio-, and stereoselectivity of the addition are discussed. I, II, X, R = H; III-V, R = Me; VI-VIII, R = Ph.It was reliably established [1, 2] that acid-catalyzed solvation of bicyclo[1.1.0]butane compounds is initiated by proton attack exclusively at the bridgehead position; next follows solvent addition at either central or side C-C bond of the substrate. Acid-catalyzed hydromethoxylation of bicyclo[1.1.0]butane derivatives was studied most thoroughly. The chemo-and regioselectivity of the addition strongly depend on the position and electronic properties of substituents at the bicyclobutane skeleton. In particular, tricyclo[4.1.0.0 2,7 ]-heptane (I), which may be regarded as specific 2,4-dialkyl-substituted bicyclobutane, takes up methanol molecule with strict chemoslelectivity at the side C-C bond [3] with formation of norcarane structure II, whereas the addition to bicyclobutane itself was not chemoselective: both cyclobutyl and cyclopropylcarbinyl derivatives were formed [3,4]. Specific stereochemistry was revealed in acid-catalyzed addition of CH 3 OD to tricycloheptane I [3]. Electrophilic attack by D + on the side bicyclobutane C-C bond is characterized by complete stereoselectivity: two diastereoisomeric 2-methoxynorcaranes are formed, in which the deuterium atom occupies the endo-7 position. This means that the lack of strict stereoselectivity in the hydromethoxylation of compound I is related to the absence of selectivity at the stage of nucleophilic attack by the alcohol on intermediate 2-norcaranyl cation.1-Methyltricycloheptane III reacts with methanol in a similar way under metal complex catalysis: cleavage of the side C 2 -C 7 bond gives rise to two diastereoisomeric 2-methoxy-1-methylnorcaranes IVa and IVb (90%) together with 6-methoxy-1-methylcycloheptene (V) (10%) [5] (Scheme 1). The major products of acid-

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“…The reaction mixture obtained from tricycloheptane XI contained no sulfone XXIII (an analog of norpinane XVII); even traces of XXIII were not detected by GC-MS. An authentic sample of XXIII [10] remained unchanged upon prolonged keeping in methanol at 20°C in the presence of a catalytic amount of perchloric acid (Scheme 3).…”

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Chemo-, regio-, and stereoselectivity in acid-catalyzed hydromethoxylation of tricyclo[4.1.0.02,7]hept-1-yl and 7-methyltricyclo[4.1.0.02,7]hept-1-yl phenyl sulfones

et al. 2010

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“…For instance, by this procedure nona-1,3-diene was obtained in 72% yield proceeding from 1-(bromomethylsulfonyl)oct-1-ene. We showed in [6] that the treatment with the typical Michael reagents, enolates of CH-acids, of bromomethyl β-styryl sulfone led to the cyclization initiated by Michael addition giving tetrahydrothiophene S,S-dioxide derivative.…”

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New example of Ramberg-Böcklund reaction initiated by Michael addition

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Only isolated cases were reported [1-4] on the synthesis of functionalized olefins from α-haloalkyl vinyl sulfones through Ramberg-Bo .. cklund reaction initiated by Michael addition. The limitations of this reaction evidently depend both on the structure of the initial substrate and on the nature of the used reagent. For instance, it was established in [5] that the treatment with potassium tert-butylate, a strong base but a weak nucleophile, of α-haloalkyl vinyl sulfones containing an allyl hydrogen atom promoted the so-called vinylogic Ramberg-Bo .. cklund reaction leading to the formation of conjugated dienes. For instance, by this procedure nona-1,3-diene was obtained in 72% yield proceeding from 1-(bromomethylsulfonyl)oct-1-ene. We showed in [6] that the treatment with the typical Michael reagents, enolates of CH-acids, of bromomethyl β-styryl sulfone led to the cyclization initiated by Michael addition giving tetrahydrothiophene S,S-dioxide derivative.We report here that at treating 1-(bromomethylsulfonyl)cyclohex-1-ene (I) with sodium dimethyl malonate (20°C, 17 h) from the three mentioned possible reaction routes proceeds the one consisting in the Ramberg-Bo .. cklund reaction initiated by Michael addition:The functionalized derivative of methylenecyclohexane II is obtained. Unsaturated sulfone I was obtained in a two-stage process involving the addition of BrCH 2 SO 2 Br to cyclohexene (CH 2 Cl 2 , 10°C, 24 h, no special initiation was required) and the dehydrobromination of the adduct in a water-dioxane solution of Na 2 CO 3 at heating (50°C, 30 h). SO 2 CH 2 Br CH 2 CH(CO 2 Me) 2(1) BrCH 2 SO 2 Br (2) Na 2 CO 3 CH 2 (CO 2 Me) 2 NaH, THF I IIThe structure of compound II was confirmed by IR, 1 H and 13 C NMR spectra. In particular, in the 1 H NMR spectrum two diastereotopic methoxycarbonyl groups were found with the signals at 3.65 and 3.71 ppm that in the 13 C NMR spectrum gave rise to the signals at 52.3, 52.4 (OMe) and 168.7, 168.9 (C=O) ppm. The same groups appeared in the IR spectrum as four strong stretching vibrations bands ν C=O at 1732, 1740, 1748, and 1755 cm -1 .We are planning to establish in future whether this new example of the Ramberg-Bo .. cklund reaction that we have discovered is of a general character in the series of 1-bromomethylsulfonylcycloalkenes. 1-(Bromomethylsulfonyl)cyclohex-1-ene (I). Yield 54%, mp 55-56°C (hexane-ether, 3:1). IR spectrum, ν, cm -1 : 3036 m, 2959 m, 2936 m, 1640 m, 1308 s, 1300 s, 1142 v.s, 764 m, 606 m, 594 m, 521 m. 1 H NMR spectrum, δ, ppm: 1.62-1.74 m (2H), 1.76-1.88 m (2H), 2.32-2.41 m (4H), methylene protons of the ring; 4.32 s (2H, SO 2 CH 2 ), 7.08 br.s (1H, CH=). 13 C NMR spectrum, δ, ppm: 20.6, 21.8, 23.8, 25.7; 40.9 (SO 2 CH 2 ); 134.9 and 144.5 (C=C). Found, %: C 35.10; H 4.68. C 7 H 11 BrO 2 S.

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“…The minor component of the product mixture, sulfone IV was identified by comparing with an authentic sample[2] by GLC and NMR spectroscopy.The major , exo-2-H, exo-4-H, 3-H), 2.42-2.57 m (2H, endo-2-H, endo-4-H), 2.92 br.t (2H, 1-H, 5-H, J = 5.6 Hz), 3.13 t (1H, anti-7-H, J = 5.6 Hz), 3.83 t (1H, exo-6-H, J = 5.6 Hz), 7.58 t (2H, H arom , J = 7.6 Hz), 7.66 t (1H, H arom , J = 7.6 Hz), 7.90 d (2H, H arom , J = 7.6 Hz). 13 C NMR spectrum, δ C , ppm: 13.…”

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Azidosulfonation of tricyclo[4.1.0.02,7]heptane

et al. 2010

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ChemInform Abstract: Functionalization of Tricyclo(4.1.0.02,7)heptanes by Phenylsulfonylbromination‐Dehydrobromination.

Cited by 4 publications

References 0 publications

Chemo-, regio-, and stereoselectivity in acid-catalyzed hydromethoxylation of tricyclo[4.1.0.02,7]hept-1-yl and 7-methyltricyclo[4.1.0.02,7]hept-1-yl phenyl sulfones

Chemo-, regio-, and stereoselectivity in acid-catalyzed hydromethoxylation of tricyclo[4.1.0.02,7]hept-1-yl and 7-methyltricyclo[4.1.0.02,7]hept-1-yl phenyl sulfones

New example of Ramberg-Böcklund reaction initiated by Michael addition

Azidosulfonation of tricyclo[4.1.0.02,7]heptane

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