A Convenient Synthesis of 4-Homoisotwistane

Takaishi, Naotake; Inamoto, Yoshiaki; Aigami, Koji; Tsuchihashi, Kiyoshi; Ikeda, Hiroshi

doi:10.1080/00397917408062077

Cited by 14 publications

(13 citation statements)

References 5 publications

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“…,33,36,40,41,44, 46,50,52, 61, 63, 6716,30,31, 32,33,34,35,36, 48, 49 52 16, 22, 26, 27, 29, 33, 34, 60, 61, 62 60 16, 25, 26, 30, 31, 32, 37, 43, 48, 49, 63 25, 28, 35, 36, 60, 61 61 13, 25, 26, 27, 37, 44, 51, 62, 63, 67, 68 2, 20, 25, 33, 61 62 13, 25, 28, 29, 37, 38, 52, 61, 63, 67, 68 3, 4, 26, 35, 36, 62 63 33, 34, 35, 36, 40, 46, 47, 51, 52, 56, 59, 60, 61, 62 Paths involving bond alignment factor between approximately 60 and 120°are excluded. See text and footnote 34.…”

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The mechanisms of carbonium ion rearrangements of tricycloundecanes elucidated by empirical force field calculations

Ōsawa¹,

Aigami²,

Takaishi³

et al. 1977

J. Am. Chem. Soc.

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The mechanisms of carbonium ion rearrangements of tricycloundecanes elucidated by empirical force field calculations

Ōsawa¹,

Aigami²,

Takaishi³

et al. 1977

J. Am. Chem. Soc.

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“…However, it can be stored for months under nitrogen in a refrigerator. Hydroboration-hydrogen peroxide oxidation19•20 of the olefin 8 gave a mixture of 23% 7 and 77% 4homoisotwistan-2-exo-ol (9) in 77 % yield. The alcohols were easily separable on conventional preparative VPC.…”

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confidence: 99%

Biologically active polycycloalkanes. 2. Antiviral 4-homoisotwistane derivatives

Aigami¹,

Inamoto²,

Takaishi³

et al. 1976

J. Med. Chem.

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New derivatives of 4-homoisotwistane (tricyclo[5.3.1.0(3,8)]undecane) (3), the olefin (8), bromide (4), alcohols (7,9,11, and 14), ketone (10), acid (12), esters (13, 18a, and 18b), amides (5, 16, and 19a-d), nitrile (20), and amines and their hydrochlorides (6, 17, and 21), were prepared, and antiviral activities of these compounds were determined in vitro on a monolayer culture of chick embryo fibroblasts against Newcastle disease virus. 4-Homoisotwist-3-ylamine hydrochloride (6) and 4-homoisotwist-3-ylmethylamine hydrochloride (21) were found 30-50 times more potent than amantadine hydrochloride in this assay. Methods of preparing the test compounds included those functionalization reactions of 3 which revealed many interesting features of the reactivity of the recently discovered polycyclic hydrocarbon 3.

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“…The combined organic layer and ether extracts were washed with saturated sodium chloride solution and dried over anhydrous sodium sulfate. After removal of the solvent under slightly diminished pressure at room temperature, the residue was fractionally distilled to give 22.5 g (50%) of 3,4-dichloro-6,7-exo-trimethylenebicyclo[3.2.1]oct-2-ene: bp 138-140°(5 mm); n25•6D 1.5320; ir 2945, 2850, 1620 (C=C), 1320, 1050, 958, 798, 693 cm"1; 4H nmr 0.9-3.0 (m, 12), 4.15 (d, 1, J = 3 Hz, CHC1), 6.12 (d, 1, J = 7 Hz, C=CH): mass spectrum m/e (rel intensity) 218 (3), 216 (4), 115 (14), 114 (9), 113 (41), 112 (17), 77 (29), 69 (100), 68 (15), 67 (19), 41 (14).…”

Section: -Homoisotwistane (3)mentioning

confidence: 99%

“…Thus 2 was isomerized to 3 in a high yield in the presence of sulfuric acid. 17 Slow catalysis by Br0nsted acid made easier the study of time-conversion relationships in the rearrangement. Further isomerizations of isolated intermediates revealed the presence of some quasi-equilibriums.…”

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4-Homoisotwistane, 6,7-exo-trimethylenebicyclo[3.2.1]octane, and homoadamantane as intermediates in Broensted acid catalyzed adamantane rearrangement of tricycloundecanes

Takaishi¹,

Inamoto²,

Aigami³

1975

J. Org. Chem.

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8]undecane) (3), 6,7-exo-triinethylenebicyclo[3.2.1]octane (4), and homoadamantane (5), together with several, as yet unidentified tricycloundecanes, were discovered to be intermediates in the adamantane rearrangement of 2,3-exo-tetramethylenenorbornane (1) and 2,3-trimethylenebicyclo-[2.2.2]octane (2). 13C nmr spectroscopy was the main tool in the structure determination of 3 and 4. The structure of 4 was further confirmed by comparison with an independently synthesized authentic specimen. Br0nsted acids (trifluoromethanesulfonic acid and sulfuric acid) were found to catalyze the rearrangement of these tricycloundecane precursors with almost quantitative yields of the products, the catalysis being milder and more specific than that by aluminum halides. A high yield synthesis of 3 was accomplished by a selective rearrangement of 2 catalyzed by sulfuric acid, An outline of the reaction scheme was deduced from the product studies of these Br0nsted acid catalyzed rearrangements.Acid-catalyzed isomerization of polycyclic saturated hydrocarbons to adamantanes (so-called adamantane rearrangement) has been widely studied since the discovery of the reaction by Schleyer.1 Elucidation of the mechanism of

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A Convenient Synthesis of 4-Homoisotwistane

Cited by 14 publications

References 5 publications

The mechanisms of carbonium ion rearrangements of tricycloundecanes elucidated by empirical force field calculations

The mechanisms of carbonium ion rearrangements of tricycloundecanes elucidated by empirical force field calculations

Biologically active polycycloalkanes. 2. Antiviral 4-homoisotwistane derivatives

4-Homoisotwistane, 6,7-exo-trimethylenebicyclo[3.2.1]octane, and homoadamantane as intermediates in Broensted acid catalyzed adamantane rearrangement of tricycloundecanes

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