title: Asymmetric Catalysis with a Mechanically Point-Chiral Rotaxane.
abstract: Mechanical point-chirality in a [2]rotaxane is utilized for asymmetric catalysis. Stable enantiomers of the rotaxane result from a bulky group in the middle of the thread preventing a benzylic amide macrocycle shuttling between different sides of a prochiral center, creating point chirality in the vicinity of a secondary amine group. The resulting mechanochirogenesis delivers enantioselective organocatalysis via both enamine (up to 71:29 er) and iminium (up to 68:32 er) activation modes.
authors.affiliation: School of Chemistry, University of Manchester , Oxford Road, Manchester M13 9PL, United Kingdom.
authors.forename: Yusuf
authors.initials: Y
authors.lastname: Cakmak
authors.affiliation: School of Chemistry, University of Manchester , Oxford Road, Manchester M13 9PL, United Kingdom.
authors.forename: Sundus
authors.initials: S
authors.lastname: Erbas-Cakmak
authors.affiliation: School of Chemistry, University of Manchester , Oxford Road, Manchester M13 9PL, United Kingdom.
authors.forename: David A
authors.initials: DA
authors.lastname: Leigh
references.citation: Angew Chem Int Ed Engl. 1999 Dec 3;38(23):3528-3530
references.pmid: 10602231
references.citation: J Am Chem Soc. 2002 May 22;124(20):5656-7
references.pmid: 12010036
references.citation: Nature. 2003 Aug 21;424(6951):915-8
references.pmid: 12931181
references.citation: J Am Chem Soc. 2004 Mar 24;126(11):3438-9
references.pmid: 15025467
references.citation: J Am Chem Soc. 2006 Mar 29;128(12):4058-73
references.pmid: 16551115
references.citation: Angew Chem Int Ed Engl. 2006 Nov 6;45(43):7296-9
references.pmid: 17029314
references.citation: Chem Commun (Camb). 2006 Sep 21;(35):3714-6
references.pmid: 17047821
references.citation: Proc Natl Acad Sci U S A. 2006 Dec 26;103(52):19647-51
references.pmid: 17172453
references.citation: J Am Chem Soc. 2007 Nov 21;129(46):14452-7
references.pmid: 17973382
references.citation: Chem Rev. 2007 Dec;107(12):5471-569
references.pmid: 18072803
references.citation: J Am Chem Soc. 2008 Feb 13;130(6):1836-8
references.pmid: 18201092
references.citation: Science. 2008 Dec 12;322(5908):1668-71
references.pmid: 19074344
references.citation: Angew Chem Int Ed Engl. 2002 May 17;41(10):1790-3
references.pmid: 19750719
references.citation: Chem Commun (Camb). 2010 Mar 21;46(11):1920-2
references.pmid: 20198253
references.citation: J Am Chem Soc. 2010 Apr 7;132(13):4954-9
references.pmid: 20230033
references.citation: J Am Chem Soc. 2010 Aug 11;132(31):10741-7
references.pmid: 20681706
references.citation: Org Lett. 2011 Aug 5;13(15):3774-7
references.pmid: 21711007
references.citation: Angew Chem Int Ed Engl. 2011 Aug 8;50(33):7524-8
references.pmid: 21744450
references.citation: Angew Chem Int Ed Engl. 2012 May 21;51(21):5166-9
references.pmid: 22504844
references.citation: J Am Chem Soc. 2012 May 23;134(20):8321-3
references.pmid: 22524156
references.citation: Angew Chem Int Ed Engl. 2013 Jan 14;52(3):960-3
references.pmid: 23184655
references.citation: Science. 2013 Jan 11;339(6116):189-93
references.pmid: 23307739
references.citation: Chem Soc Rev. 2014 Jan 7;43(1):99-122
references.pmid: 24071686
references.citation: Nat Chem. 2013 Nov;5(11):945-51
references.pmid: 24153373
references.citation: Chem Commun (Camb). 2014 May 25;50(40):5128-42
references.pmid: 24434901
references.citation: J Am Chem Soc. 2014 Apr 2;136(13):4817-20
references.pmid: 24559064
references.citation: J Am Chem Soc. 2014 Apr 2;136(13):4905-8
references.pmid: 24649824
references.citation: J Am Chem Soc. 2014 Apr 16;136(15):5811-4
references.pmid: 24678971
references.citation: J Am Chem Soc. 2014 Nov 5;136(44):15775-80
references.pmid: 25285667
references.citation: Chem Rev. 2015 Aug 12;115(15):7398-501
references.pmid: 25734835
references.citation: J Am Chem Soc. 2015 Jun 24;137(24):7656-9
references.pmid: 26061430
references.citation: Chem Rev. 2015 Sep 23;115(18):10081-206
references.pmid: 26346838
references.citation: Angew Chem Int Ed Engl. 2015 Nov 9;54(46):13545-9
references.pmid: 26387887
references.citation: Nat Chem. 2016 Jan;8(1):8-9
references.pmid: 26673258
references.citation: Chem Sci. 2015 Jan 1;6(1):140-143
references.pmid: 28553462