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syn-Diastereoselective Homoaldol Reactions: γ-Hydroxyalkylation of (Z)-2-Butenyl Carbamates and Synthesis of β,γ-cis-Di- and -Trisubstituted γ-Lactones

✍ Scribed by Prof. Dr. Dieter Hoppe; Dr. Florian Lichtenberg


Publisher
John Wiley and Sons
Year
1984
Tongue
English
Weight
352 KB
Volume
23
Category
Article
ISSN
0044-8249

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✦ Synopsis


In the crystal, the molecule has C, symmetry (Fig. ); its conformation essentially corresponds to that which, according to MNDO calculations and NMR data, is the more stable of the two conformations in The benzene ring has an unsymmetric boat conformation, whose most striking characteristic is the marked bending of the "bow" (Fig. ; al =26.8"); to our knowledge this is the strongest deviation from planarity known so far in a benzene ring. The angle at the "stern" is smaller (a2 = 12 O ) , and the sum al+a2=38.8" is close to that found in the [6]paracyclophane system (41.3 '[Ia1, 38.9 '[Ib1). A remarkable feature is the large angle Dl = 48 O ; the strain at the bridgehead carbon atoms C-6 and C-10 also manifests itself in marked pyramidalization (sum of the bond angles: 354").