Enantiospecific preparation of gem-dimethylcyclopropane fused cycloheptanes via valence tautomerization of 3,4-homotropilidene under thermodynamic and kinetic control

Tetrahedron Letters

Volumn 37, Issue 40, 1996, Pages 7303-7306

  Sugimura, Takashi ^a   Futagawa, Tohru ^a   Katagiri, Toshifumi ^a   Nishiyama, Norio ^a   Tai, Akira ^a  

^a UNIVERSITY OF HYOGO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

BICYCLO COMPOUND; CYCLOPROPANE DERIVATIVE;

ARTICLE; CHEMICAL REACTION KINETICS; CHIRALITY; DRUG SYNTHESIS; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; REACTION ANALYSIS; THERMODYNAMICS;

EID: 0030607227     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)01654-1     Document Type: Article

References (29)

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18. 1/2 = 3.25 hours).
19. 3 gave 21 as a single diastereomer (26.4% yield). Treatment of 4b with butyl lithium followed by quenching with water also afforded 21 (ca. 40% yield). The diastereomer at the 8-position was not detected at all in both cases.
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21. 3 at -78 °C in 25-30% yield. Sec-butyl lithium treatment of 21 at -72 °C followed by quenching with water also afforded 6 as a sole product (ca. 70%).
22. 8. The results of the MO-calculation study agreed with the present study. The heat of formation of 5, 4b, and the corresponding rearranged products, 6 and 7b, were calculated in the transoid and cisoid confonners using the AM-1 method. The TBS group in the compounds was replaced by a f-butyl group to simplify the calculation. Since an energy minimum was not obtained in the case of cisoid-4b, the energy shown in parentheses was calculated using the structure of cisoid-5. Heat of formation (kcal/mol), 5: transoid -2.30, cisoid 0.78. 6: cisoid -12.37, transoid -16.92. 4b: transoid 14.72, cisoid (39.39). 7b: cisoid 18.18, transoid 12.37.
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26. D = 215).
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28. (b) Tai, A.; Kikukawa, T.; Sugimura, T.; Inoue, Y.; Abe, S.; Osawa, T.; Harada, T. Bull. Chem. Soc. Jpn. 1994, 67, 2473-7. Both enantiomers of DMHD are also available from Wako Pure Chemical Industries, Ltd., Japan.
29. 9