Regioselective Ring Opening of N,N-dibenzylaziridinium Ion and Advantageous Method for DNA Aptamer Selection
- 발행기관 서강대학교 일반대학원
- 지도교수 이원구
- 발행년도 2009
- 학위수여년월 2009. 2
- 학위명 석사
- 실제URI http://www.dcollection.net/handler/sogang/000000045072
- 본문언어 한국어
초록/요약
Regioselective Ring Opening of N,N-dibenzylaziridinium Ion : The Hydride-induced Ring Opening of The Aziridinium Ions The regioselectivity in the ring opening of N,N-dibenzyl- 2-substituted aziridinium ions is dependent on various factors including reaction solvents and nucleophiles. When the nucleophile is bromide (Br-) regioselective C-2 opening product was formed predominantly. We treated the brominated ring-opening product with various hydride reagents in different reaction conditions. The smaller and the harder nucleophile such as “H-” (NaBH4 in THF) reacts at C-3 of the quarternary aziridinium ion. The Hydride- induced ring opening of the aziridinium ions comprises a novel aspect in aziridinium chemistry and the use of different nucleophiles may provide interesting new insights into the chemistry of aziridinium ions. Advantageous Method for DNA Aptamer Selection : Synthesis of DKP (Diketopiperazine) on Silica Bead Aptamers are ssDNA or RNA oliginucleotides with very high affinity for their target. They bind to the target with high selectivity and specificity because of specific three-dimensional shape. The synthesis of 2,5-diketopiperazine analogues were accomplished in high yields by peptide coupling reaction. DKP of Pro-Phe, Pro-Tyr can be used as aptamers.
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Regioselective Ring Opening of N,N-dibenzylaziridinium Ion = 1
ABSTRACT = 2
Ⅰ. INTRODUCTION = 3
Ⅱ. RESULT and DISCUSSION = 6
Ⅲ. EXPERIMENTAL SECTION = 11
1. Procedure for preparation of N-Benzyl-N-(2(R)-bromo-3-(4-methoxyphenoxy)propyl)-1(R)-N-phenylethyl)amine(6a-6f) = 13
1-1. N-Benzyl-N-(2(R)-bromo-3-(4-methoxyphenoxy)propyl)-(1(R)-N-phenylethyl)amine (6a) = 14
1-2. N-Benzyl-N-(2(R)-bromo-3-(3-chlorophenoxy)propyl)-(1(R)-N-phenylethyl)amine (6b) = 15
1-3. N-Benzyl-N-(2(R)-bromo-3-(4-chlorophenoxy)propyl)-(1(R)-N-phenylethyl)amine (6c) = 16
1-4. N-Benzyl-N-(2(R)-bromo-3-phenoxy)propyl)-(1(R)-N-phenylethyl)amine (6d) = 17
1-5. N-Benzyl-N-(2(R)-bromo-3-methoxypropyl)-(1(R)-N-phenylethyl)amine (6e) = 18
1-6. N-Benzyl-N-(2(R)-bromo-3-ethoxypropyl)-(1(R)-N-phenylethyl)amine (6f) = 19
2. Procedure for preparation of the ring opening reaction with hydride nucleophile on NaBH4 in THF (7a-7f) = 20
2-1. 2-amino-1-(p-methoxyphenyloxy)propane (7a) = 21
2-2. 2-amino-1-(m-chlorophenyloxy)propane (7b) = 22
2-3. 2-amino-1-(p-chlorophenyloxy)propane (7c) = 23
2-4. 2-amino-1-phenyloxypropane (7d) = 24
2-5. 2-amino-1-methoxypropane (7e) = 25
2-6. 2-amino-1-ethoxypropane (7f) = 26
3. Procedure for preparation of the ring opening reaction with hydride nucleophile on LiAlH4 in THF (8) = 27
3-1. aminopropene (8) = 28
Advantageous Method for DNA Aptamer Selection = 29
ABSTRACT = 30
Ⅰ. INTRODUCTION = 31
Ⅱ. RESULT and DISCUSSION = 33
Ⅲ. EXPERIMENTAL SECTION = 45
1. Procedure for preparation of N-Boc-L-Phenylalanyl-L-4-hydroxyproline methyl ester (16) = 47
2. Procedure for preparation of N-Boc-L-Tyrosine-L-proline methyl ester (17) = 49
3. Procedure for preparation of 2,5-diketopiperazines (18) = 51
4. Procedure for preparation of 2,5-diketopiperazines (19) = 53
5-1. DKP coupled with linker (20) = 55
5-2. DKP coupled with linker (21) = 56
Ⅳ. REFERENCE = 57