Topologically Controlled Syntheses of Unimolecular Oligo[ n ]catenanes.

Autor:	Colley ND; Department of Chemistry, Washington University, St. Louis, Missouri 63130, United States., Nosiglia MA; Department of Chemistry, Washington University, St. Louis, Missouri 63130, United States., Tran SL; Department of Chemistry, Washington University, St. Louis, Missouri 63130, United States., Harlan GH; Department of Chemistry, Washington University, St. Louis, Missouri 63130, United States., Chang C; Department of Chemistry, Washington University, St. Louis, Missouri 63130, United States., Li R; Department of Chemistry, Washington University, St. Louis, Missouri 63130, United States., Delawder AO; Department of Chemistry, Washington University, St. Louis, Missouri 63130, United States., Zhang Y; Department of Chemistry, Washington University, St. Louis, Missouri 63130, United States., Barnes JC; Department of Chemistry, Washington University, St. Louis, Missouri 63130, United States.
Jazyk:	angličtina
Zdroj:	ACS central science [ACS Cent Sci] 2022 Dec 28; Vol. 8 (12), pp. 1672-1682. Date of Electronic Publication: 2022 Nov 29.
DOI:	10.1021/acscentsci.2c00697
Abstrakt:	Catenanes are a well-known class of mechanically interlocked molecules that possess chain-like architectures and have been investigated for decades as molecular machines and switches. However, the synthesis of higher-order catenanes with multiple, linearly interlocked molecular rings has been greatly impeded by the generation of unwanted oligomeric byproducts and figure-of-eight topologies that compete with productive ring closings. Here, we report two general strategies for the synthesis of oligo[ n ]catenanes that rely on a molecular "zip-tie" strategy, where the "zip-tie" is a central core macrocycle precursor bearing two phenanthroline (phen) ligands to make odd-numbered oligo[ n ]catenanes, or a preformed asymmetric iron(II) complex consisting of two macrocycle precursors bearing phen and terpyridine ligands to make even-numbered oligo[ n ]catenanes. In either case, preformed macrocycles or [2]catenanes are threaded onto the central "zip-tie" core using metal templation prior to ring-closing metathesis (RCM) reactions that generate several mechanical bonds in one pot. Using these synthetic strategies, a family of well-defined linear oligo[ n ]catenanes were synthesized, where n = 2, 3, 4, 5, or 6 interlocked molecular rings, and n = 6 represents the highest number of linearly interlocked rings reported to date for any isolated unimolecular oligo[ n ]catenane. Competing Interests: The authors declare the following competing financial interest(s): The authors filed a non-provisional patent containing part of the work described in this manuscript. (© 2022 The Authors. Published by American Chemical Society.)
Databáze:	MEDLINE
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