2013年9月
Synthesis and Self-Assembly of NCN-Pincer Pd-Complex-Bound Norvalines
CHEMISTRY-A EUROPEAN JOURNAL
- 巻
- 19
- 号
- 37
- 開始ページ
- 12356
- 終了ページ
- 12375
- 記述言語
- 英語
- 掲載種別
- 研究論文(学術雑誌)
- DOI
- 10.1002/chem.201301513
- 出版者・発行元
- WILEY-V C H VERLAG GMBH
The NCN-pincer Pd-complex-bound norvalines Boc-D/L-[PdCl(dpb)]Nva-OMe (1) were synthesized in multigram quantities. The molecular structure and absolute configuration of 1 were unequivocally determined by single-crystal X-ray structure analysis. The robustness of 1 under acidic/basic conditions provides a wide range of N-/C-terminus convertibility based on the related synthetic transformations. Installation of a variety of functional groups into the N-/C-terminus of 1 was readily carried out through N-Boc- or C-methyl ester deprotection and subsequent condensations with carboxylic acids, (RCOOH)-C-1, or amines, (RNH2)-N-2, to give the corresponding N-/C-functionalized norvalines R-1-D/L-[PdCl(dpb)]Nva-R-2 2-9. The dipeptide bearing two Pd units 10 was successfully synthesized through the condensation of C-free 1 with N-free 1. The robustness of these Pd-bound norvalines was adequately demonstrated by the preservation of the optical purity and Pd unit during the synthetic transformations. The lipophilic Pd-bound norvalines L-2, Boc-L-[PdCl(dpb)]Nva-NH-n-C11H23, and L-4, n-C4H9CO-L-[PdCl(dpb)]Nva-NH-n-C11H23, self-assembled in aromatic solvents to afford supramolecular gels. The assembled structures in a thermodynamically stable single crystal of L-2 and kinetically stable supramolecular aggregates of L-2 were precisely elucidated by cryo-TEM, WAX, SAXS, UV/Vis, IR analyses, and single-crystal X-ray crystallography. An antiparallel -sheet-type aggregate consisting of an infinite one-dimensional hydrogen-bonding network of amide groups and -stacking of PdCl(dpb) moieties was observed in the supramolecular gel fiber of L-2, even though discrete dimers are assembled through hydrogen bonding in the thermodynamically stable single crystal of L-2. The disparate DSC profiles of the single crystal and xerogel of L-2 indicate different thermodynamics of the molecular assembly process.
- リンク情報
-
- DOI
- https://doi.org/10.1002/chem.201301513
- J-GLOBAL
- https://jglobal.jst.go.jp/detail?JGLOBAL_ID=201302283818555292
- PubMed
- https://www.ncbi.nlm.nih.gov/pubmed/23907820
- Web of Science
- https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000323731200028&DestApp=WOS_CPL
- ID情報
-
- DOI : 10.1002/chem.201301513
- ISSN : 0947-6539
- eISSN : 1521-3765
- J-Global ID : 201302283818555292
- PubMed ID : 23907820
- Web of Science ID : WOS:000323731200028