The Size-Accelerated Kinetic Resolution of Secondary Alcohols.
acylation
asymmetric catalysis
kinetic resolution
molecular recognition
noncovalent interactions
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
11 01 2021
11 01 2021
Historique:
received:
26
08
2020
pubmed:
23
10
2020
medline:
23
10
2020
entrez:
22
10
2020
Statut:
ppublish
Résumé
The factors responsible for the kinetic resolution of alcohols by chiral pyridine derivatives have been elucidated by measurements of relative rates for a set of substrates with systematically growing aromatic side chains using accurate competitive linear regression analysis. Increasing the side chain size from phenyl to pyrenyl results in a rate acceleration of more than 40 for the major enantiomer. Based on this observation a new catalyst with increased steric bulk has been designed that gives enantioselectivity values of up to s=250. Extensive conformational analysis of the relevant transition states indicates that alcohol attack to the more crowded side of the acyl-catalyst intermediate is favoured due to stabilizing CH-π-stacking interactions. Experimental and theoretical results imply that enantioselectivity enhancements result from accelerating the transformation of the major enantiomer through attractive non-covalent interactions (NCIs) rather than retarding the transformation of the minor isomer through repulsive steric forces.
Identifiants
pubmed: 33090615
doi: 10.1002/anie.202011687
pmc: PMC7821155
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
774-778Informations de copyright
© 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
Références
Nat Chem. 2012 Oct;4(10):817-24
pubmed: 23000995
J Chem Theory Comput. 2016 Oct 11;12(10):4778-4792
pubmed: 27564403
Chemistry. 2016 Dec 23;22(52):18916-18922
pubmed: 27775200
J Chem Theory Comput. 2011 Mar 8;7(3):625-632
pubmed: 21516178
Chem Sci. 2017 Feb 1;8(2):864-877
pubmed: 28572898
Chem Sci. 2015 Jul 1;6(7):4358-4364
pubmed: 29218207
Angew Chem Int Ed Engl. 2015 Oct 12;54(42):12274-96
pubmed: 26262562
J Org Chem. 2009 Oct 16;74(20):7633-43
pubmed: 19813764
Chemistry. 2019 Mar 21;25(17):4452-4459
pubmed: 30657217
Nature. 2017 Mar 29;543(7647):637-646
pubmed: 28358089
Org Biomol Chem. 2018 May 2;16(17):3121-3126
pubmed: 29561025
Angew Chem Int Ed Engl. 2016 Jan 18;55(3):912-6
pubmed: 26632979
Angew Chem Int Ed Engl. 2014 Oct 27;53(44):11818-21
pubmed: 25124842
Angew Chem Int Ed Engl. 2001 Aug 3;40(15):2818-2821
pubmed: 11500876
J Chem Phys. 2006 Jan 21;124(3):034108
pubmed: 16438568
Proc Natl Acad Sci U S A. 2010 Nov 30;107(48):20678-85
pubmed: 20956302
Phys Rev B Condens Matter. 1988 Jan 15;37(2):785-789
pubmed: 9944570
Angew Chem Int Ed Engl. 2007;46(48):9335-8
pubmed: 17990256
Org Biomol Chem. 2018 Aug 8;16(31):5643-5652
pubmed: 30039152
Chem Sci. 2018 Jun 29;9(31):6509-6515
pubmed: 30310581
Chemistry. 2005 Aug 5;11(16):4751-7
pubmed: 15924289
J Chem Phys. 2010 Apr 21;132(15):154104
pubmed: 20423165
J Comput Chem. 2012 Feb 15;33(5):580-92
pubmed: 22162017
Acc Chem Res. 2017 Mar 21;50(3):609-615
pubmed: 28945415
J Chem Phys. 2013 Oct 7;139(13):134101
pubmed: 24116546
Acc Chem Res. 2000 Jun;33(6):412-20
pubmed: 10891059
J Am Chem Soc. 2012 Jun 6;134(22):9390-9
pubmed: 22568686
Science. 2003 Aug 29;301(5637):1196-202
pubmed: 12947189
J Am Chem Soc. 2017 Jan 11;139(1):492-516
pubmed: 28029251
Chem Soc Rev. 2014 Mar 7;43(5):1660-733
pubmed: 24356298
Phys Chem Chem Phys. 2005 Sep 21;7(18):3297-305
pubmed: 16240044
Chem Rev. 2006 Aug;106(8):3210-35
pubmed: 16895325
Acc Chem Res. 2013 Apr 16;46(4):979-89
pubmed: 22827883
J Chem Phys. 2013 Jan 21;138(3):034106
pubmed: 23343267
J Am Chem Soc. 2009 Oct 28;131(42):15358-74
pubmed: 19778044
Acc Chem Res. 2016 May 17;49(5):1061-9
pubmed: 27110641
Angew Chem Int Ed Engl. 2011 Dec 23;50(52):12639-42
pubmed: 22025456
Angew Chem Int Ed Engl. 2021 Jan 11;60(2):774-778
pubmed: 33090615
Org Lett. 2015 Jun 19;17(12):3066-9
pubmed: 26046695