Size-Induced Inversion of Selectivity in the Acylation of 1,2-Diols.
acylation
anhydrides
noncovalent interaction
organocatalysis
regioselectivity
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783
Informations de publication
Date de publication:
23 Dec 2021
23 Dec 2021
Historique:
received:
31
05
2021
pubmed:
26
10
2021
medline:
28
12
2021
entrez:
25
10
2021
Statut:
ppublish
Résumé
Relative rates for the Lewis base-catalyzed acylation of aryl-substituted 1,2-diols with anhydrides differing in size have been determined by turnover-limited competition experiments and absolute kinetics measurements. Depending on the structure of the anhydride reagent, the secondary hydroxyl group of the 1,2-diol reacts faster than the primary one. This preference towards the secondary hydroxyl group is boosted in the second acylation step from the monoesters to the diester through size and additional steric effects. In absolute terms the first acylation step is found to be up to 35 times faster than the second one for the primary alcohols due to neighboring group effects.
Identifiants
pubmed: 34693585
doi: 10.1002/chem.202101905
pmc: PMC9299827
doi:
Substances chimiques
Alcohols
0
Anhydrides
0
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
18084-18092Subventions
Organisme : Deutsche Forschungsgemeinschaft
ID : ZI 436/17-1
Informations de copyright
© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
Références
Chemistry. 2006 Jul 24;12(22):5779-84
pubmed: 16718731
Chemistry. 2021 Dec 23;27(72):18084-18092
pubmed: 34693585
Angew Chem Int Ed Engl. 2010 Jul 12;49(30):5165-9
pubmed: 20568073
Chem Sci. 2018 Jun 29;9(31):6509-6515
pubmed: 30310581
J Org Chem. 2015 Sep 18;80(18):9279-91
pubmed: 26317990
Org Biomol Chem. 2004 Jun 7;2(11):1563-72
pubmed: 15162204
Nat Prod Rep. 2014 Mar;31(3):318-34
pubmed: 24468713
J Phys Chem B. 2009 May 7;113(18):6378-96
pubmed: 19366259
Br J Surg. 2021 Sep 27;108(9):1056-1063
pubmed: 33761533
J Org Chem. 2000 Feb 25;65(4):996-1002
pubmed: 10814046
J Am Chem Soc. 2007 Oct 24;129(42):12890-5
pubmed: 17902666
J Org Chem. 2013 Nov 15;78(22):11618-22
pubmed: 24164588
Chemistry. 2018 Oct 9;24(56):15052-15058
pubmed: 30070735
Bioinformatics. 2006 Dec 15;22(24):3067-74
pubmed: 17032683
J Chem Phys. 2006 Jan 21;124(3):034108
pubmed: 16438568
Angew Chem Int Ed Engl. 2015 Oct 5;54(41):11966-70
pubmed: 26384855
J Chem Theory Comput. 2011 Mar 8;7(3):625-632
pubmed: 21516178
Chem Rev. 2018 Dec 12;118(23):11457-11517
pubmed: 30507165
J Org Chem. 2021 Feb 19;86(4):3456-3489
pubmed: 33555864
Phys Rev B Condens Matter. 1988 Jan 15;37(2):785-789
pubmed: 9944570
Molecules. 2016 May 17;21(5):
pubmed: 27196888
Acc Chem Res. 2015 Feb 17;48(2):295-305
pubmed: 25493641
J Chem Phys. 2013 Oct 7;139(13):134101
pubmed: 24116546
Nat Commun. 2015 Jun 18;6:7512
pubmed: 26085287
Angew Chem Int Ed Engl. 2016 Feb 12;55(7):2493-7
pubmed: 26766239
Nature. 2007 Mar 22;446(7134):404-8
pubmed: 17377577
Angew Chem Int Ed Engl. 2006 Aug 25;45(34):5616-9
pubmed: 16858713
J Org Chem. 2012 Feb 3;77(3):1457-67
pubmed: 22283732
J Am Chem Soc. 2010 May 12;132(18):6498-506
pubmed: 20394428
Phys Chem Chem Phys. 2005 Sep 21;7(18):3297-305
pubmed: 16240044
J Am Chem Soc. 2012 May 16;134(19):8260-7
pubmed: 22533533
Org Lett. 2004 Mar 18;6(6):945-8
pubmed: 15012071
J Chem Phys. 2013 Jan 21;138(3):034106
pubmed: 23343267
J Org Chem. 2014 Sep 5;79(17):8134-42
pubmed: 25102271
Angew Chem Int Ed Engl. 2021 Jan 11;60(2):774-778
pubmed: 33090615
Angew Chem Int Ed Engl. 2010;49(2):262-310
pubmed: 20014082
Angew Chem Int Ed Engl. 2015 Oct 5;54(41):12134-8
pubmed: 26384020
Carbohydr Res. 1976 Oct;51(1):C1-C4
pubmed: 1000522
J Org Chem. 2007 Feb 16;72(4):1499-502
pubmed: 17288394
J Med Chem. 2015 Mar 12;58(5):2367-77
pubmed: 25671771
Org Biomol Chem. 2018 Aug 8;16(31):5591-5597
pubmed: 30027976
J Am Chem Soc. 2016 May 11;138(18):6002-9
pubmed: 27104625