- Email: [email protected]
A solid-phase synthesis of oligodeoxyribonucleotides and their analogues using deoxyribonucleoside phosphorobisdiethylamidite intermediates
243 On the other hand, the polymers containing a thymine photodimer in the main chain underwent dissociation of the thymine photodimers upon irradiation by UV light (250 nm), leading to breakage of the polymer chains. These polymers could be used as positive type photoresists and high resolution (0.3 /~m) was demonstrated. Polyamides containing thymine photodimer units in the main chains showed excellent resolution values and behaved as positive photoresists. It is concluded that polymers containing pyrimidine bases displayed high resolution and high sensitivity when used in both negative and positive photoresists formulations. 1 2 3 4
M.J. Moghaddam, S. Hozumi, Y. Inaki and K. Takemoto, J. Polym. Sci. Polym. Chem. Ed., 26 (1988) 27, 3297. M.J. Moghaddam, K. Kanbara, S. Hozumi, Y. Inaki and K. Takemoto, Polym. J., 22 (1990) 369. M.J. Moghaddam, Y. Inaki and K. Takemoto, Polym. J., 22 (1990) 468. Y. Inaki, K. Moghaddam and K. Takemoto, ACS Symp. Set., 412 (1989) 303.
Application of Guanidine-Hanging Polystyrene to Synthetic Chemistry T a m o t s u Y a m a m o t o , M i t s u r u F u j i m o t o a n d M a s a h i k o K o b o r i , Kanto Gakuin University, Japan Guanidines [unsubstituted and monocyclic (2-propylaminoimidazoline)] have been grafted onto crosslinked polystyrene chains by reaction with poly(p-chloromethyl styrene) (content = 56%) in DMF. The degrees of grafting were 50-56%. To examine the applicability of the guanidine-hanging polymers (PSG) to synthetic chemistry, dehydrobromination of dibromide of diethyl maieate and esterification of benzoic acid with alkyl halides and polymerization of aldehydes using PSG's were tried to give monodehydrobrominated product, alkyl benzoates and polymers of aldehydes, respectively. To be submitted to Polym. J. or React. Polym.
A Solid-Phase Synthesis of Oligodeoxyribonucleotides and Their Analogues Using Deoxyribonucleoside Phosphorobisdiethylamidite Intermediates K a z u s h i g e Y a m a n a , Y o s h i t a k a Nishijima, H i r o a k i O z a k i *, H i d e h i k o N a k a n o , O s a m u S a n g e n a n d T a k e o S h i m i d z u *, Department of Applied Chemistry, Himeji Institute of Technology, 2167
Shosha, Himeji 671-22, Japan and * Division of Molecular Engineering, Kyoto University, Sakyoku, Kyoto 606, Japan The phosphite triether approach has proven to be useful for the solid-phase synthesis of oligodeoxyribonucleotides [1]. Deoxyribonucleoside fl-cyanoethyl and methyl phosphoramidites have been employed as intermediates for the synthesis. On the other hand, deoxyribonucleoside H-phosphonate has been shown to be useful for preparation of oligodeoxyribonucleotide analogues possessing modified backbones. We have recently developed a new approach by using deoxyribonucleoside phosphorobisdiethylamidites for oligonucleotide synthesis [2]. An interesting feature of this approach is that the chain elongation reactions on a solid support proceed via phosphorodiethylamidite which could be converted to various modified phosphate backbones. It is therefore expected that our approach provides a convenient method for the preparation of DNA analogues with modified backbones as well as DNA oligomers. The phosphorobisamidite intermediates were obtained by reaction of the protected deoxyribonucleoside with tris(diethylamino)phosphine or bis(diethylamino)phosphorochloridite as a phosphylating reagent and were used directly for a solid-phase synthesis. DNA oligomers were obtained with a high coupling efficiency (average > 97%). Direct oxidation of the phosphoramidite formed after coupling with t-butyl hydroperoxide or S8 gave DNA analogues of phosphorodiethylamidate or phosphorodiethylthioamidate, respectively. The reaction of the amidite with alcohol followed by oxidation yielded phosphotriester analogues. 1 R.L. Letsinger and W.B. Lunsford, J. Am. Chem. Soc., 98 (1976) 3655; M.D. Matteucci and M.H. Caruthers, ibid., 103 (1981) 3185; T. Atkinson and M. Smith, in M.J. Gait (Ed.), Oligonucleotide Synthesis: A Practical Approach, IRL Press, Oxford, 1985. pp. 35-81. 2 K. Yamana, Y. Nishijima, A. Oka, H. Nakano, O. Sangen, H. Ozaki and T. Shimidzu, Tetrahedron, 45 (1989) 4135.
M.J. Moghaddam, S. Hozumi, Y. Inaki and K. Takemoto, J. Polym. Sci. Polym. Chem. Ed., 26 (1988) 27, 3297. M.J. Moghaddam, K. Kanbara, S. Hozumi, Y. Inaki and K. Takemoto, Polym. J., 22 (1990) 369. M.J. Moghaddam, Y. Inaki and K. Takemoto, Polym. J., 22 (1990) 468. Y. Inaki, K. Moghaddam and K. Takemoto, ACS Symp. Set., 412 (1989) 303.
Application of Guanidine-Hanging Polystyrene to Synthetic Chemistry T a m o t s u Y a m a m o t o , M i t s u r u F u j i m o t o a n d M a s a h i k o K o b o r i , Kanto Gakuin University, Japan Guanidines [unsubstituted and monocyclic (2-propylaminoimidazoline)] have been grafted onto crosslinked polystyrene chains by reaction with poly(p-chloromethyl styrene) (content = 56%) in DMF. The degrees of grafting were 50-56%. To examine the applicability of the guanidine-hanging polymers (PSG) to synthetic chemistry, dehydrobromination of dibromide of diethyl maieate and esterification of benzoic acid with alkyl halides and polymerization of aldehydes using PSG's were tried to give monodehydrobrominated product, alkyl benzoates and polymers of aldehydes, respectively. To be submitted to Polym. J. or React. Polym.
A Solid-Phase Synthesis of Oligodeoxyribonucleotides and Their Analogues Using Deoxyribonucleoside Phosphorobisdiethylamidite Intermediates K a z u s h i g e Y a m a n a , Y o s h i t a k a Nishijima, H i r o a k i O z a k i *, H i d e h i k o N a k a n o , O s a m u S a n g e n a n d T a k e o S h i m i d z u *, Department of Applied Chemistry, Himeji Institute of Technology, 2167
Shosha, Himeji 671-22, Japan and * Division of Molecular Engineering, Kyoto University, Sakyoku, Kyoto 606, Japan The phosphite triether approach has proven to be useful for the solid-phase synthesis of oligodeoxyribonucleotides [1]. Deoxyribonucleoside fl-cyanoethyl and methyl phosphoramidites have been employed as intermediates for the synthesis. On the other hand, deoxyribonucleoside H-phosphonate has been shown to be useful for preparation of oligodeoxyribonucleotide analogues possessing modified backbones. We have recently developed a new approach by using deoxyribonucleoside phosphorobisdiethylamidites for oligonucleotide synthesis [2]. An interesting feature of this approach is that the chain elongation reactions on a solid support proceed via phosphorodiethylamidite which could be converted to various modified phosphate backbones. It is therefore expected that our approach provides a convenient method for the preparation of DNA analogues with modified backbones as well as DNA oligomers. The phosphorobisamidite intermediates were obtained by reaction of the protected deoxyribonucleoside with tris(diethylamino)phosphine or bis(diethylamino)phosphorochloridite as a phosphylating reagent and were used directly for a solid-phase synthesis. DNA oligomers were obtained with a high coupling efficiency (average > 97%). Direct oxidation of the phosphoramidite formed after coupling with t-butyl hydroperoxide or S8 gave DNA analogues of phosphorodiethylamidate or phosphorodiethylthioamidate, respectively. The reaction of the amidite with alcohol followed by oxidation yielded phosphotriester analogues. 1 R.L. Letsinger and W.B. Lunsford, J. Am. Chem. Soc., 98 (1976) 3655; M.D. Matteucci and M.H. Caruthers, ibid., 103 (1981) 3185; T. Atkinson and M. Smith, in M.J. Gait (Ed.), Oligonucleotide Synthesis: A Practical Approach, IRL Press, Oxford, 1985. pp. 35-81. 2 K. Yamana, Y. Nishijima, A. Oka, H. Nakano, O. Sangen, H. Ozaki and T. Shimidzu, Tetrahedron, 45 (1989) 4135.