The synthesis of ring systems via ally/nickel mesylates
The synthesis of ring systems via ally/nickel mesylates
Cyclohexa-l,5-diene was prepared by the reaction of the bismethane sulphonate ester of hexadeca-2,14-diene-1,16-diol with tetracarbonyl nickel in dime thylformamide at 50°C. Cyclotetradeca-1,5-diene and cyclododeca-1,5-diene were also obtained in this way. Cyclohexadeca-l,5-diene was prepared in higher yield by reaction of the bis-methane sulphonate ester of hexadeca-2, 14-diene-1,16-diol wits bis-(cycloocta-1,5-diene)nickel in dimethylformamide at 0 C. Cycloheptadea -5-en-Ii-one was obtained by hydrolysis of the methyl enol ether resulting from bis(cycloocta-i,5-diene) nickel promoted cyclisation of 3-methoxyheptadeca-2,15-diene-1,17-diol-1,17-bis-methane sulphonate ester. 3-tert.-Butyldimethylsilyloxyheptadeca-2,15-diene-1,17diol failed to provide cycloheptadeca-5-en-l-one using the same methodology. The extension of this methodology to the synthesis of zearalenone, a metabolite of Gibberella Zeae was initiated. The synthesis of cyclic ketone, 4,8,12-trimethylcyclotetradeca3,7,11-triene-l-one, which possesses the basic skeleton of the cembranolides was attempted. The synthesis was based on the dialkylation of 1,3-dithiane leading to the bis-allylic alcohol necessary for derivatisation prior to bis-(cycloocta-1,5-diene)nickel promoted cyclisation.
University of Southampton
1982
Johnston, Brian Henry
(1982)
The synthesis of ring systems via ally/nickel mesylates.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Cyclohexa-l,5-diene was prepared by the reaction of the bismethane sulphonate ester of hexadeca-2,14-diene-1,16-diol with tetracarbonyl nickel in dime thylformamide at 50°C. Cyclotetradeca-1,5-diene and cyclododeca-1,5-diene were also obtained in this way. Cyclohexadeca-l,5-diene was prepared in higher yield by reaction of the bis-methane sulphonate ester of hexadeca-2, 14-diene-1,16-diol wits bis-(cycloocta-1,5-diene)nickel in dimethylformamide at 0 C. Cycloheptadea -5-en-Ii-one was obtained by hydrolysis of the methyl enol ether resulting from bis(cycloocta-i,5-diene) nickel promoted cyclisation of 3-methoxyheptadeca-2,15-diene-1,17-diol-1,17-bis-methane sulphonate ester. 3-tert.-Butyldimethylsilyloxyheptadeca-2,15-diene-1,17diol failed to provide cycloheptadeca-5-en-l-one using the same methodology. The extension of this methodology to the synthesis of zearalenone, a metabolite of Gibberella Zeae was initiated. The synthesis of cyclic ketone, 4,8,12-trimethylcyclotetradeca3,7,11-triene-l-one, which possesses the basic skeleton of the cembranolides was attempted. The synthesis was based on the dialkylation of 1,3-dithiane leading to the bis-allylic alcohol necessary for derivatisation prior to bis-(cycloocta-1,5-diene)nickel promoted cyclisation.
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Published date: 1982
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Local EPrints ID: 460431
URI: http://eprints.soton.ac.uk/id/eprint/460431
PURE UUID: 8e2057cf-3dd3-41a9-b6ae-a7a5b0d2be18
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Date deposited: 04 Jul 2022 18:22
Last modified: 04 Jul 2022 18:22
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Author:
Brian Henry Johnston
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