The Intramolecular Diels-Alder Reactions of Silyl Substituted Masked o-Benzoquinones
碩士 === 國立清華大學 === 化學系 === 89 === Abstract This thesis describes the studies on intramolecular Diels-Alder reactions of masked o-benzoquinones (MOBs). The masked o-benzoquinones, 6-methoxy-4-trimethylsilyl-6-alkenyloxy-2,4-cyclo -hexadienones 49a-c, were generated in situ by th...
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ndltd-TW-089NTHU00650462016-01-29T04:33:40Z http://ndltd.ncl.edu.tw/handle/08956305800648412408 The Intramolecular Diels-Alder Reactions of Silyl Substituted Masked o-Benzoquinones 矽烷取代基掩飾鄰苯之分子內Diels-Alder反應研究 Po-Yin Lin 林泊吟 碩士 國立清華大學 化學系 89 Abstract This thesis describes the studies on intramolecular Diels-Alder reactions of masked o-benzoquinones (MOBs). The masked o-benzoquinones, 6-methoxy-4-trimethylsilyl-6-alkenyloxy-2,4-cyclo -hexadienones 49a-c, were generated in situ by the oxidation with DAIB of the corresponding 2-methoxyphenols 44 and alkenols 48. The intramolecular Diels-Alder reactions of MOB 49 provided desired adducts 50 in good yields. Oxidation of 2-methoxyphenols 44 using DAIB, followed by intramolecular Diels-Alder reaction with dienophiles 55, was carried out to produce the tricyclo[4.3.1.03,7]decenones 57 and cis-decalins 58; The tricyclo[4.3.1.03,7]decenones 57 can be converted into cis-decalins 58 via Cope rearrangement in equilibrium. The analyses of the calculation by RHF/STO-3G method suggest that the enthalpy difference between the tricyclo[4.3.1.03,7]decenones 57 and cis-decalins 58 is about 3 Kcal/mol. So the Cope rearrangement process is in equilibrium. Using the vinylmagnesium bromide and cerous chloride complex as addition reagent, addition to tricyclo[4.3.1.03,7]decenones 50 furnished a mixture of the diastereo-selective alcohols 69 and 70. Chun-Chen Liao 廖俊臣 2001 學位論文 ; thesis 150 zh-TW |
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碩士 === 國立清華大學 === 化學系 === 89 === Abstract
This thesis describes the studies on intramolecular Diels-Alder reactions of masked o-benzoquinones (MOBs). The masked o-benzoquinones, 6-methoxy-4-trimethylsilyl-6-alkenyloxy-2,4-cyclo -hexadienones 49a-c, were generated in situ by the oxidation with DAIB of the corresponding 2-methoxyphenols 44 and alkenols 48. The intramolecular Diels-Alder reactions of MOB 49 provided desired adducts 50 in good yields.
Oxidation of 2-methoxyphenols 44 using DAIB, followed by intramolecular Diels-Alder reaction with dienophiles 55, was carried out to produce the tricyclo[4.3.1.03,7]decenones 57 and cis-decalins 58; The tricyclo[4.3.1.03,7]decenones 57 can be converted into cis-decalins 58 via Cope rearrangement in equilibrium. The analyses of the calculation by RHF/STO-3G method suggest that the enthalpy difference between the tricyclo[4.3.1.03,7]decenones 57 and cis-decalins 58 is about 3 Kcal/mol. So the Cope rearrangement process is in equilibrium.
Using the vinylmagnesium bromide and cerous chloride complex as addition reagent, addition to tricyclo[4.3.1.03,7]decenones 50 furnished a mixture of the diastereo-selective alcohols 69 and 70.
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author2 |
Chun-Chen Liao |
author_facet |
Chun-Chen Liao Po-Yin Lin 林泊吟 |
author |
Po-Yin Lin 林泊吟 |
spellingShingle |
Po-Yin Lin 林泊吟 The Intramolecular Diels-Alder Reactions of Silyl Substituted Masked o-Benzoquinones |
author_sort |
Po-Yin Lin |
title |
The Intramolecular Diels-Alder Reactions of Silyl Substituted Masked o-Benzoquinones |
title_short |
The Intramolecular Diels-Alder Reactions of Silyl Substituted Masked o-Benzoquinones |
title_full |
The Intramolecular Diels-Alder Reactions of Silyl Substituted Masked o-Benzoquinones |
title_fullStr |
The Intramolecular Diels-Alder Reactions of Silyl Substituted Masked o-Benzoquinones |
title_full_unstemmed |
The Intramolecular Diels-Alder Reactions of Silyl Substituted Masked o-Benzoquinones |
title_sort |
intramolecular diels-alder reactions of silyl substituted masked o-benzoquinones |
publishDate |
2001 |
url |
http://ndltd.ncl.edu.tw/handle/08956305800648412408 |
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