A chiral macrocycle for the stereoselective synthesis of mechanically planar chiral rotaxanes and catenanes

Active-template auxiliary methodologies have previously been developed for the stereoselective synthesis of chiral interlocked molecules in which the mechanical bond provides the sole stereogenic unit. To date however, the covalent auxiliary has been included in the half-axle components (rotaxanes) or pre-macrocycle components (catenanes), and thus mechanically chiral rotaxane and catenane syntheses rely on different chiral components. Here we present a single, simple amino acid-derived macrocycle that mediates the formation of both catenanes and rotaxanes in excellent stereoselectivity. We demonstrate the flexibility of our approach through the stereoselective synthesis of all three isomers of a co-conformationally mechanically planar chiral [3]rotaxane.

catenanes, chirality, rotaxanes, SDG9: Industry innovation and infrastructure, stereoselective

10.1016/j.chempr.2023.01.009

2451-9308

1195-1207

Zhang, Shu

1ed472af-dec8-4424-b9f8-882a911fc537

Rubio, Arnau Rodriguez

8e967297-87a7-4197-bdaf-fe9bd7955502

Saady, Abed

fcdef21d-2f85-4740-bf09-0cfa775278cf

Tizzard, Graham J.

8474c0fa-40df-43a6-a662-7f3c4722dbf2

Goldup, Stephen

0a93eedd-98bb-42c1-a963-e2815665e937

11 May 2023

Zhang, Shu

1ed472af-dec8-4424-b9f8-882a911fc537

Rubio, Arnau Rodriguez

8e967297-87a7-4197-bdaf-fe9bd7955502

Saady, Abed

fcdef21d-2f85-4740-bf09-0cfa775278cf

Tizzard, Graham J.

8474c0fa-40df-43a6-a662-7f3c4722dbf2

Goldup, Stephen

0a93eedd-98bb-42c1-a963-e2815665e937

Zhang, Shu, Rubio, Arnau Rodriguez, Saady, Abed, Tizzard, Graham J. and Goldup, Stephen (2023) A chiral macrocycle for the stereoselective synthesis of mechanically planar chiral rotaxanes and catenanes. Chem, 9 (5), 1195-1207. (doi:10.1016/j.chempr.2023.01.009).

Record type: Article

Abstract

Text

rvsd MS Chem chiral bipy clean - Accepted Manuscript

Available under License Creative Commons Attribution Non-commercial No Derivatives.

Download (1MB)

More information

Accepted/In Press date: 16 January 2023

e-pub ahead of print date: 15 February 2023

Published date: 11 May 2023

Additional Information: Funding Information: The authors dedicate this article to Professor Sir Fraser Stoddart on the occasion of his 80 th birthday. S.M.G. thanks the European Research Council (Consolidator Grant agreement no. 724987 ) and the Royal Society for a Research Fellowship ( RSWF\FT\180010 ). A.S. thanks the Council for Higher Education of Israel for a personal fellowship. Funding Information: The authors dedicate this article to Professor Sir Fraser Stoddart on the occasion of his 80th birthday. S.M.G. thanks the European Research Council (Consolidator Grant agreement no. 724987) and the Royal Society for a Research Fellowship (RSWF\FT\180010). A.S. thanks the Council for Higher Education of Israel for a personal fellowship. S.M.G. conceived the project and secured project funding. S.Z. designed macrocycle 1a and carried out initial synthetic investigations with rotaxanes 4, 5–7, and 12 and catenanes 14–16 and obtained single crystals of 4b for SCXRD analysis. A.R.-R. completed these investigations, synthesized rotaxanes 8 and 9, and obtained single crystals of 4a and 15 for SCXRD analysis. A.R.-R. and A.S. synthesized rotaxanes 20. A.S. obtained single crystals of 18 for SCXRD analysis. A.R.-R. led the preparation of the supplemental information and contributed to the stereochemical analysis of all products. G.J.T. collected and analyzed all SCXRD data reported. S.M.G. wrote the manuscript with input from all authors. All authors contributed to the reviewing and editing of the manuscript. The authors declare no competing interests. Publisher Copyright: © 2023 The Author(s)

Keywords: catenanes, chirality, rotaxanes, SDG9: Industry innovation and infrastructure, stereoselective

Learn more about School of Chemistry research Learn more about Institute for Life Sciences research