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Synlett 2003(3): 0349-0352
DOI: 10.1055/s-2003-37126
LETTER
© Georg Thieme Verlag Stuttgart · New York

Design, Synthesis, and Self-Assembly of Parallel Cyclobolaphile that Contains Four Amide Groups as a Linkage between Polar Head Groups and Hydro­carbon Chain: A Mimetic of Archaeal Membrane Lipid

Kazuhiro Miyawaki, Atsuhiro Harada, Toshiyuki Takagi, Motonari Shibakami*
Institute for Materials and Chemical Process, Institute of Advanced Industrial Science and Technology (AIST), Central 5th, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
Fax: +81(298)614547; e-Mail: moto.shibakami@aist.go.jp;
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Publication History

Received 29 December 2002
Publication Date:
07 February 2003 (online)

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Abstract

Chiral 52-membered macrocyclic compound has been synthesized by utilizing intramolecular cyclization under Eglinton conditions [Cu(OAc)2, pyridine]. Three structural features include: (i) two hydrocarbon chains containing diacetylene, (ii) a linkage that is composed of amide group, and (iii) two polar head groups. Self-assembly of this compound in a mixture of chloroform-methanol (1:1) produced organogel. Transmission electron micrograph revealed that UV-irradiated gel is featured by nanosize helicity.

Key words

archaeal lipid - diacetylene - mimetic - amide - helical ribbon - nanostructure - polymerization - organogel

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14

Our synthetic scheme should provide optically pure compound 1. Our reason for this is 2-fold. First, the first step [8a] that can lead to racemization retained the stereochemical configuration of l-serine methyl ester hydrochloride {2: [α]D 21 +4.99 (c 3.55, CHCl3), Lit. [8a] [α]D +4.7 (c 1.2, CHCl3)}. Second, intermediates (2-7) and the desired product (1) do not include carbonyl group that can cause epimerization at the chiral center.