Abstract
The asymmetric reduction of poly(isopropenyl methyl ketone ) via hydrosilylation gave a new optically active polymer, poly(3-methyl-3-buten-2-ol). The hydrosilylation was carried out with diphenylsilane and a rhodium(I) catalyst containing a chiral phosphine ligand. The effects of the reaction conditions on the optical rotation of the polymer formed were studied in detail. The highest specific rotation ([α]D20) reached was +18.4°, and was attained by the hydrosilylation in 1,4-dioxane at 30°C. On the other hand, both pinacolone (as a monomeric ketone) and a 1: 1 copolymer of isopropenyl methyl ketone with styrene produced the corresponding alcohols having negative small rotations (ca. −3°).
Similar content being viewed by others
Article PDF
References
P. Pino, Adv. Polym. Sci., 4, 393 (1965).
T. Tsuruta, J. Polym. Sci., D, 6, 179 (1972).
J. W. ApSimon and R. P. Seguin, Tetrahedron, 35, 2797 (1979).
D. Valentine, Jr. and J. W. Scott, Synthesis, 329 (1978).
H. B. Kagan, Pure Appl. Chem., 43, 401 (1975).
T. Masuda and J. K. Stille, J. Am. Chem. Soc., 100, 268 (1978).
T. Masuda and H. Ibuki, Polym. J., 12, 143 (1980).
E. F. Landau and F. P. Irany, J. Org. Chem., 12, 422 (1947).
A. van der Ent and A. L. Onderdelinden, Inorg. Synth., 14, 92 (1973).
H. B. Kagan and T. P. Dang, J. Am. Chem. Soc., 94, 6429 (1972).
R. A. Benkeser, H. Landesman, and D. J. Foster, J. Am. Chem. Soc., 74, 648 (1952).
I. Ojima, K. Yamamoto, and M. Kumada, “Aspects of Homogeneous Catalysis,” Vol. 3, R. Ugo, Ed., D. Reidel Publishers Co., Donarecht-Holland, 1977.
Y. Okamoto, K. Suzuki, K. Ohta, K. Hatada, and H. Yuki, J. Am. Chem. Soc., 101, 4763 (1979).
K. Takemoto and M. Miyata, J. Macromol. Sci., Rev. Macromol. Chem., C18, 83 (1980).
M. Kawai, T. Masuda, and T. Higashimura, unpublished data.
L. Merle-Aubry and Y. Merle, Eur. Polym. J., 16, 227 (1980).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Kawai, M., Masuda, T. Asymmetric Reduction of Poly(isopropenyl methyl ketone) via Rhodium(I)-Catalyzed Hydrosilylation. Polym J 13, 573–577 (1981). https://doi.org/10.1295/polymj.13.573
Issue Date:
DOI: https://doi.org/10.1295/polymj.13.573