Copolymerization of 7-methylenebicyclo[4.1.0]heptane with carbon monoxide initiated by optically active palladium complexes

Daisuke Takeuchi, Ayami Yasuda, Takeshi Okada, Junpei Kuwabara, Kohtaro Osakada, Katsuhiko Tomooka

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Seven Pd-complexes with optically active bis[dihydroxazole]-type ligands promote asymmetric alternating copolymerization of 7-methylenebicyclo[4.1.0] heptane with CO, which produces an optically active polyketone, -[C(=CH 2 )-CO-C 6 H 10 ] n -. The reaction under increased CO pressure (>5 atm) affords a polymer that contains monomer units with the cis-cyclohexane-1,2-diyl group almost exclusively. The polyketone exhibits positive or negative optical rotation depending on the Pd-complex. The highest and lowest [α] D 25 of the polymer obtained are +68.9 and -76.1, respectively. Addition of dibutylcuprate to a solution of the polymer in the presence of Me 3 SiCl transforms the enone groups of the polymer to silyl enol ether groups, which are ozonized to (silyloxy)oxirane moieties.

Original languageEnglish
Pages (from-to)1574-1588
Number of pages15
JournalHelvetica Chimica Acta
Volume89
Issue number8
DOIs
Publication statusPublished - Sep 14 2006
Externally publishedYes

Fingerprint

Heptanes
Palladium
Heptane
copolymerization
Carbon Monoxide
heptanes
Carbon monoxide
carbon monoxide
Copolymerization
palladium
Polymers
polymers
Optical rotation
Optical Rotation
Ethylene Oxide
Cyclohexane
cyclohexane
Ether
Ethers
ethers

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Biochemistry
  • Drug Discovery
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Copolymerization of 7-methylenebicyclo[4.1.0]heptane with carbon monoxide initiated by optically active palladium complexes. / Takeuchi, Daisuke; Yasuda, Ayami; Okada, Takeshi; Kuwabara, Junpei; Osakada, Kohtaro; Tomooka, Katsuhiko.

In: Helvetica Chimica Acta, Vol. 89, No. 8, 14.09.2006, p. 1574-1588.

Research output: Contribution to journalArticle

Takeuchi, Daisuke ; Yasuda, Ayami ; Okada, Takeshi ; Kuwabara, Junpei ; Osakada, Kohtaro ; Tomooka, Katsuhiko. / Copolymerization of 7-methylenebicyclo[4.1.0]heptane with carbon monoxide initiated by optically active palladium complexes. In: Helvetica Chimica Acta. 2006 ; Vol. 89, No. 8. pp. 1574-1588.
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