Stereocontrol of intramolecular Diels-Alder reactions: Synthetic studies and transition structure modeling with C5-substituted 1,3,8-nonatrienes and nonadienynes
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作者:
Turner, CI
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机构:Univ New S Wales, Sch Chem, Sydney, NSW 2052, Australia
Turner, CI
Williamson, RM
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机构:Univ New S Wales, Sch Chem, Sydney, NSW 2052, Australia
Williamson, RM
Paddon-Row, MN
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Univ New S Wales, Sch Chem, Sydney, NSW 2052, AustraliaUniv New S Wales, Sch Chem, Sydney, NSW 2052, Australia
Paddon-Row, MN
[1
]
Sherburn, MS
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机构:Univ New S Wales, Sch Chem, Sydney, NSW 2052, Australia
Sherburn, MS
机构:
[1] Univ New S Wales, Sch Chem, Sydney, NSW 2052, Australia
[2] Univ New S Wales, Sch Chem, Sydney, NSW 2052, Australia
[3] Massey Univ, Inst Fundamental Sci, Palmerston North, New Zealand
An investigation into the endo/exo selectivity and iz-diastereofacial selectivity of ester-tethered intramolecular Diels-Alder reactions is reported. High levels of exo selectivity are realized with terminally substituted dienophiles, and high Lk rr-diastereofacial selectivities are induced by the presence of a bulky dioxolanyl substituent at the allylic position of the tether. Precursors 19S, 20S, and 21S, readily prepared from glucose, provide densely functionalized bicyclic lactones of predictable stereochemistry in high yields in enantiomerically pure form upon thermolysis at 110 degreesC. B3LYP/6-31G(d) theory provides good descriptions of transition structures for these reactions and allows an understanding of the formation of the major cycloadducts.