TY - JOUR
T1 - Rearrangements of Tricyclo[5.3.1.01,7]undecatrienide Anion
T2 - Circumambulation and Cleavage of the Cyclopropane Ring
AU - Oda, Mitsunori
AU - Masaki, Yoshimi
AU - Okazaki, Yoshimi
AU - Kajioka, Takanori
AU - Morita, Yasufumi
AU - Miyatake, Ryuta
AU - Kuroda, Shigeyasu
N1 - Funding Information:
At the time of the EWGT constitu tion in Maffiiers, one of the first goals of the Group Elected Board was to obtain from the European Community the inclusion of gene therapy as a specific subject for funding in the contest of European funding programs. "Gene Therapy in Europe", has been entering a new phase in 1995 and two major achievements should be recorded: {1 ) Research Funding of European Labs. Somatic gene therapy appears as a priority in the 4th framework programmes of the DGXII both in "Biomed 2" and "Biotechnology"; this represents a significant step forward, since until now official recognition of this field of research by the European Parliament and the Commissions of the European Union was highly disputed. This is expected to positively affect gene therapy research and will foster new international collaborations. Significant funding from the Commission of the European Communities (DGXII) provides financial support at a level otherwise not accessible. Programmes supported by the DGXII favour collaboration between various European teams towards providing additional quality through so-called "European added value". (2) Regulation. The CPMP \[Committee for Proprietary Medicinal Products) has approved (last December 1994) a final draft of the "Gene therapy products: quality aspects in the production of vectors and genetically modified somatic cells" thereby releasing guidelines for putting gene therapy products on the market s (DG III/3477/92. Ad hoc Working Party on Biotechnology/Pharmacy: Production and quality control of medicinal products derived by recombinant DNA technology, revision 1994.) z The primary purpose of this document is to provide guidance on the data required to support applications for marketing authoriza-
PY - 1998/8
Y1 - 1998/8
N2 - Reaction of tricyclo[5.3.1.01,7]undeca-2,4,9-triene with butyllithium in tetrahydrofuran-hexamethylphosphoric triamide at -78 °C and subsequent quenching of the resulted dark red reaction mixture with water or methanol gave tricyclo[6.3.0.01,3]undeca-5,7,9-triene (4) as the sole isolable product. It was also found that quenching of the anion solution with deuterium oxide under the same conditions caused stereoselective incorporation of deuterium atom. On the other hand, quenching of the anion solution with water after it was warmed to 0 °C gave a mixture of dihydromethylazulenes. The cycloadduct of the rearranged hydrocarbon 4 with 4-phenyl-3H-1,2,4-triazoline-3,5(4H)-dione was obtained and its structure was confirmed by X-ray crystallographic analysis. A driving force of the circumambulation was thought to be the creation of conjugation between the cycloheptadienide part and the five-membered ring olefin in the product on the basis of the facts that a circumambulatory rearrangement in the opposite direction, which would lead to a different product via a less conjugated tricyclic anion, was not observed, and that the anion generated from tricyclo[5.3.1.01,7]undeca-2,4-diene was reluctant to undergo the rearrangement.
AB - Reaction of tricyclo[5.3.1.01,7]undeca-2,4,9-triene with butyllithium in tetrahydrofuran-hexamethylphosphoric triamide at -78 °C and subsequent quenching of the resulted dark red reaction mixture with water or methanol gave tricyclo[6.3.0.01,3]undeca-5,7,9-triene (4) as the sole isolable product. It was also found that quenching of the anion solution with deuterium oxide under the same conditions caused stereoselective incorporation of deuterium atom. On the other hand, quenching of the anion solution with water after it was warmed to 0 °C gave a mixture of dihydromethylazulenes. The cycloadduct of the rearranged hydrocarbon 4 with 4-phenyl-3H-1,2,4-triazoline-3,5(4H)-dione was obtained and its structure was confirmed by X-ray crystallographic analysis. A driving force of the circumambulation was thought to be the creation of conjugation between the cycloheptadienide part and the five-membered ring olefin in the product on the basis of the facts that a circumambulatory rearrangement in the opposite direction, which would lead to a different product via a less conjugated tricyclic anion, was not observed, and that the anion generated from tricyclo[5.3.1.01,7]undeca-2,4-diene was reluctant to undergo the rearrangement.
UR - http://www.scopus.com/inward/record.url?scp=0345570366&partnerID=8YFLogxK
U2 - 10.1246/bcsj.71.1959
DO - 10.1246/bcsj.71.1959
M3 - 学術論文
AN - SCOPUS:0345570366
SN - 0009-2673
VL - 71
SP - 1959
EP - 1965
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
IS - 8
ER -