Chirality organization of ferrocenes bearing podand dipeptide chains: Synthesis and structural characterization

被引:175
作者
Moriuchi, T [1 ]
Nomoto, A [1 ]
Yoshida, K [1 ]
Ogawa, A [1 ]
Hirao, T [1 ]
机构
[1] Osaka Univ, Fac Engn, Dept Appl Chem, Suita, Osaka 5650871, Japan
关键词
D O I
10.1021/ja002869n
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A variety of ferrocenes bearing podand dipeptide chains have been synthesized to form an ordered structure in both solid and solution states and have been investigated by H-1 NMR, FT-IR, CD, and X-ray crystallographic analyses. Conformational enantiomerization through chirality organization was achieved by the intramolecular hydrogen bondings between the podand dipeptide chains. The single-crystal X-ray structure determination of the ferrocene 2 bearing the podand dipeptide chains (-D-Ala-D-Pro-OEt) revealed two C-2-symmetric intramolecular hydrogen bondings between CO (Ala) and NH (another Pla) of each podand dipeptide chain to induce the chirality-organized structure. The molecular structures of the ferrocene 1 composed of the podand L-dipeptide chains (-L-Ala-L-Pro-OEt) and 2 are in a good mirror image relationship, indicating that they are conformational enantiomers. An opposite helically ordered molecular arrangement was formed in the crystal packing of 2 as compared with 1. The ferrocene 2 exhibited induced circular dichroism (CD), which appeared at the absorbance of the ferrocene moiety. The mirror image of the CD signals between 1 and 2 was observed, suggesting that the chirality-organized structure via intramolecular hydrogen bondings is present even in solution. The ferrocene 4 bearing the podand dipeptide chains (-Gly-L-Leu-OEt) also showed an ordered structure in the crystal based on two intramolecular hydrogen bondings between CO (Gly) and NH (another Gly) of each podand dipeptide chain, together with intermolecular hydrogen bondings between CO adjacent to the ferrocene unit and NH (neighboring Leu) to create the highly organized self-assembly. A different self-assembly was observed in the crystal of the ferrocene 5 composed of the podand dipeptide chains (-Gly-L-Phe-OEt), wherein each molecule is bonded to two neighboring molecules through two pairs of symmetrical intermolecular hydrogen bonds to form a 14-membered intermolecularly hydrogen-bonded ring. These ordered structures based on the intramolecular hydrogen bondings in the solution state are also confirmed by H-1 NMR and FT-IR.
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页码:68 / 75
页数:8
相关论文
共 47 条
[21]   PEPTIDOMIMETICS AND THE TEMPLATE APPROACH TO NUCLEATION OF BETA-SHEETS AND ALPHA-HELICES IN PEPTIDES [J].
KEMP, DS .
TRENDS IN BIOTECHNOLOGY, 1990, 8 (09) :249-255
[22]   SYNTHESIS OF PEPTIDE-FUNCTIONALIZED DIACYLAMINOEPINDOLIDIONES AS TEMPLATES FOR BETA-SHEET FORMATION [J].
KEMP, DS ;
BOWEN, BR .
TETRAHEDRON LETTERS, 1988, 29 (40) :5077-5080
[23]   CONFORMATIONAL-ANALYSIS OF PEPTIDE-FUNCTIONALIZED DIACYLAMINOEPINDOLIDIONES H-1-NMR EVIDENCE FOR BETA-SHEET FORMATION [J].
KEMP, DS ;
BOWEN, BR .
TETRAHEDRON LETTERS, 1988, 29 (40) :5081-5082
[24]   Synthesis and redox property of polypeptides containing L-ferrocenylalanine [J].
Kira, M ;
Matsubara, T ;
Shinohara, H ;
Sisido, M .
CHEMISTRY LETTERS, 1997, (01) :89-90
[25]   Ferrocenoyl amino acids: A synthetic and structural study [J].
Kraatz, HB ;
Lusztyk, J ;
Enright, GD .
INORGANIC CHEMISTRY, 1997, 36 (11) :2400-2405
[26]  
KYTE J, 1998, STRUCTURE PROTEIN CH
[27]   Neutral molecule receptor systems using ferrocene's ''atomic ball bearing'' character as the flexible element [J].
Li, CS ;
Medina, JC ;
Maguire, GEM ;
Abel, E ;
Atwood, JL ;
Gokel, GW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (07) :1609-1618
[28]   A MOLECULAR RECEPTOR BASED ON THE FERROCENE SYSTEM - SELECTIVE COMPLEXATION USING ATOMIC BALL-BEARINGS [J].
MEDINA, JC ;
LI, CS ;
BOTT, SG ;
ATWOOD, JL ;
GOKEL, GW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (01) :366-367
[29]   FERROCENYL IRON AS A DONOR GROUP FOR COMPLEXED SILVER IN FERROCENYLDIMETHYL[2.2]CRYPTAND - A REDOX-SWITCHED RECEPTOR EFFECTIVE IN WATER [J].
MEDINA, JC ;
GOODNOW, TT ;
ROJAS, MT ;
ATWOOD, JL ;
LYNN, BC ;
KAIFER, AE ;
GOKEL, GW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (26) :10583-10595
[30]   Characterization of ferrocene derivatives bearing podand dipeptide chains (-L-Ala-L-Pro-OR) [J].
Moriuchi, T ;
Nomoto, A ;
Yoshida, K ;
Hirao, T .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1999, 589 (01) :50-58