Inherently Chiral Calix[4]arenes Via Oxazoline Directed Ortholithiation: Synthesis and Probe of Chiral Space

Overview

Journal Beilstein J Org Chem

Specialty Chemistry

Date 2015 Jan 1

PMID 25550740

Citations 3

Authors

Simon A Herbert

Laura J van Laeren

Dominic C Castell

Gareth E Arnott

Affiliations

Soon will be listed here.

Abstract

The diastereoselective oxazoline-directed lithiation of calix[4]arenes is reported with diastereoselective ratios of greater than 100:1 in some instances. Notably, it has been found that the opposite diastereomer can be accessed via this approach merely through the choice of an alkyllithium reagent. The inherently chiral oxazoline calix[4]arenes have also been preliminarily examined as ligands in the palladium-catalyzed Tsuji-Trost allylation reaction, returning results comparable to their planar chiral ferrocene counterparts pointing towards future application of these types of compounds.

Citing Articles

Simultaneous construction of inherent and axial chirality by cobalt-catalyzed enantioselective C-H activation of calix[4]arenes.

Li T, Zhang Y, Du C, Yang D, Song M, Niu J Nat Commun. 2024; 15(1):7673.

PMID: 39242562 PMC: 11379863. DOI: 10.1038/s41467-024-52133-8.

Attempted synthesis of a -metalated calix[4]arene.

Jurisch C, Arnott G Beilstein J Org Chem. 2019; 15:1996-2002.

PMID: 31501666 PMC: 6719732. DOI: 10.3762/bjoc.15.195.

Recent applications of chiral calixarenes in asymmetric catalysis.

Durmaz M, Halay E, Bozkurt S Beilstein J Org Chem. 2018; 14:1389-1412.

PMID: 29977403 PMC: 6009176. DOI: 10.3762/bjoc.14.117.

References

Kim H, Lee M, Mutihac L, Vicens J, Kim J . Host-guest sensing by calixarenes on the surfaces. Chem Soc Rev. 2011; 41(3):1173-90. DOI: 10.1039/c1cs15169j. View

Xu Z, Zhang C, Yang Y, Chen C, Huang Z . Effective nonenzymatic kinetic resolution of racemic m-nitro-substituted inherently chiral aminocalix[4]arenes. Org Lett. 2008; 10(3):477-9. DOI: 10.1021/ol702884u. View

Sliwka-Kaszynska M, Slebioda M . Polycyclic aromatic hydrocarbons as test probes to investigate the retention behavior of 1,3-alternate calix[4]arene silica-bonded stationary phases. J Sep Sci. 2013; 37(5):543-50. DOI: 10.1002/jssc.201301038. View

Yakovenko A, Boyko V, Danylyuk O, Suwinska K, Lipkowski J, Kalchenko V . Diastereoselective lower rim (1S)-camphorsulfonylation as the shortest way to the inherently chiral calix[4]arene. Org Lett. 2007; 9(7):1183-5. DOI: 10.1021/ol0628513. View

Arrayas R, Adrio J, Carretero J . Recent applications of chiral ferrocene ligands in asymmetric catalysis. Angew Chem Int Ed Engl. 2006; 45(46):7674-715. DOI: 10.1002/anie.200602482. View

Herbert S, Castell D, Clayden J, Arnott G . Manipulating the diastereoselectivity of ortholithiation in planar chiral ferrocenes. Org Lett. 2013; 15(13):3334-7. DOI: 10.1021/ol4013734. View

Herbert S, Arnott G . Synthesis of inherently chiral calix[4]arenes: stereocontrol through ligand choice. Org Lett. 2010; 12(20):4600-3. DOI: 10.1021/ol101909f. View

Herbert S, Arnott G . An asymmetric ortholithiation approach to inherently chiral calix[4]arenes. Org Lett. 2009; 11(21):4986-9. DOI: 10.1021/ol902238p. View

Pan S, Wang D, Zhao L, Wang M . Synthesis and functionalization of inherently chiral tetraoxacalix[2]arene[2]pyridines. Org Lett. 2012; 14(24):6254-7. DOI: 10.1021/ol303019q. View

10.

Sliwka-Kaszynska M, Jaszcolt K, Anusiewicz I . 1,3-Alternate calix[4]arene-bonded silica stationary phases. Effect of calixarene skeleton substituents on the retention mechanism and column selectivity. J Sep Sci. 2009; 32(18):3107-15. DOI: 10.1002/jssc.200900330. View

11.

Xu Z, Zhang C, Zheng Q, Chen C, Huang Z . A new approach to enantiopure inherently chiral calix[4]arenes: determination of their absolute configurations. Org Lett. 2007; 9(22):4447-50. DOI: 10.1021/ol701714q. View

12.

Shirakawa S, Kimura T, Murata S, Shimizu S . Synthesis and resolution of a multifunctional inherently chiral calix[4]arene with an ABCD substitution pattern at the wide rim: the effect of a multifunctional structure in the organocatalyst on enantioselectivity in asymmetric reactions. J Org Chem. 2008; 74(3):1288-96. DOI: 10.1021/jo8024412. View

13.

Shirakawa S, Moriyama A, Shimizu S . Design of a novel inherently chiral calix[4]arene for chiral molecular recognition. Org Lett. 2007; 9(16):3117-9. DOI: 10.1021/ol071249p. View

14.

Perret F, Coleman A . Biochemistry of anionic calix[n]arenes. Chem Commun (Camb). 2011; 47(26):7303-19. DOI: 10.1039/c1cc11541c. View

15.

Harrowfield J . Calixarenes and cations. Chem Commun (Camb). 2013; 49(16):1578-80. DOI: 10.1039/c3cc38667h. View

16.

Bencini A, Coluccini C, Garau A, Giorgi C, Lippolis V, Messori L . A BINOL-based chiral polyammonium receptor for highly enantioselective recognition and fluorescence sensing of (S,S)-tartaric acid in aqueous solution. Chem Commun (Camb). 2012; 48(84):10428-30. DOI: 10.1039/c2cc35383k. View

17.

Li J, Wang L, Wang D, Zhao L, Wang M . Synthesis, resolution, structure, and racemization of inherently chiral 1,3-alternate azacalix[4]pyrimidines: quantification of conformation mobility. J Org Chem. 2014; 79(5):2178-88. DOI: 10.1021/jo500054v. View

18.

Overman L, Owen C, Zipp G . Diastereoselective lithiation of (eta6-arene)dicarbonyltriphenylphosphane chromium(0) oxazoline complexes--direct preparation of enantiopure complexes having planar chiral fragments of either configuration. Angew Chem Int Ed Engl. 2002; 41(20):3884-7. DOI: 10.1002/1521-3773(20021018)41:20<3884::AID-ANIE3884>3.0.CO;2-0. View

19.

Alavi S, Woo T, Sirjoosingh A, Lang S, Moudrakovski I, Ripmeester J . Hydrogen adsorption and diffusion in p-tert-butylcalix[4]arene: an experimental and molecular simulation study. Chemistry. 2010; 16(38):11689-96. DOI: 10.1002/chem.201000589. View

20.

Mutihac L, Lee J, Kim J, Vicens J . Recognition of amino acids by functionalized calixarenes. Chem Soc Rev. 2011; 40(5):2777-96. DOI: 10.1039/c0cs00005a. View