Secondary Orbital Effect Involving Fluorine is Responsible for Substrate-Controlled Diastereodivergence in the Catalyzed syn-aza-Henry Reaction of α-Fluoronitroalkanes.
aza-Henry reactions
density functional calculations
fluorine
mechanistic studies
organocatalysis
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783
Informations de publication
Date de publication:
25 Apr 2023
25 Apr 2023
Historique:
received:
29
12
2022
pmc-release:
25
04
2024
medline:
7
1
2023
pubmed:
7
1
2023
entrez:
6
1
2023
Statut:
ppublish
Résumé
The fluorine atom is a powerful, yet enigmatic influence on chemical reactions. True to form, fluorine was recently discovered to effect diastereodivergence in an enantioselective aza-Henry reaction, resulting in a very rare case of syn-β-amino nitroalkane products. More bewildering was the observation of an apparent hierarchy of substituents within this substrate-controlled behavior: Ph>F>alkyl. These cases have now been examined comprehensively by computational methods, including both non-fluorinated and α-fluoro nitronate additions to aldimines catalyzed by a chiral bis(amidine) [BAM] proton complex. This study revealed the network of non-covalent interactions that dictate anti- (α-aryl) versus syn-selectivity (α-alkyl) using α-fluoronitronate nucleophiles, and an underlying secondary orbital interaction between fluorine and the activated azomethine.
Identifiants
pubmed: 36607705
doi: 10.1002/chem.202204066
pmc: PMC10324543
mid: NIHMS1904292
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
e202204066Subventions
Organisme : NIGMS NIH HHS
ID : R01 GM084333
Pays : United States
Organisme : NIGMS NIH HHS
ID : GM 084333
Pays : United States
Informations de copyright
© 2023 Wiley-VCH GmbH.
Références
Org Lett. 2009 Aug 6;11(15):3310-3
pubmed: 19583199
J Am Chem Soc. 2008 Aug 20;130(33):10878-9
pubmed: 18646755
Angew Chem Int Ed Engl. 2011 Dec 9;50(50):11860-71
pubmed: 21953782
Chem Soc Rev. 2014 Jan 7;43(1):135-47
pubmed: 24162874
Nat Commun. 2017 Mar 20;8:14793
pubmed: 28317928
J Am Chem Soc. 2016 Oct 26;138(42):13794-13797
pubmed: 27749040
J Am Chem Soc. 2008 May 7;130(18):5866-7
pubmed: 18410096
Chem Rev. 2013 May 8;113(5):2887-939
pubmed: 23461586
Angew Chem Int Ed Engl. 1998 Oct 16;37(19):2580-2627
pubmed: 29711625
J Am Chem Soc. 2008 Jun 25;130(25):7955-66
pubmed: 18510320
Chemistry. 2008;14(27):8094-7
pubmed: 18655092
Org Biomol Chem. 2016 Oct 12;14(40):9588-9597
pubmed: 27714327
J Am Chem Soc. 2004 Mar 24;126(11):3418-9
pubmed: 15025457
Chem Sci. 2011 Jan 1;2(6):1076-1079
pubmed: 22708054
Chem Sci. 2022 Feb 14;13(9):2614-2623
pubmed: 35356677
Angew Chem Int Ed Engl. 2022 Aug 22;61(34):e202207966
pubmed: 35716396
Chem Soc Rev. 2016 Oct 21;45(20):5441-5454
pubmed: 27499359
Acc Chem Res. 2018 Jul 17;51(7):1701-1710
pubmed: 29894155
J Org Chem. 2016 Apr 15;81(8):3286-95
pubmed: 27008440
J Am Chem Soc. 2007 Apr 25;129(16):4900-1
pubmed: 17394322
Chem. 2019 May 9;5(5):1248-1264
pubmed: 32766460
Molecules. 2021 Mar 31;26(7):
pubmed: 33807341
J Org Chem. 2014 Aug 1;79(15):6913-38
pubmed: 25017623
J Am Chem Soc. 2017 Apr 26;139(16):5627-5639
pubmed: 28384402
J Am Chem Soc. 2010 Apr 7;132(13):4925-34
pubmed: 20218689
J Org Chem. 2013 Nov 1;78(21):10605-16
pubmed: 24127627
J Org Chem. 2021 Nov 5;86(21):15606-15617
pubmed: 34669416
Angew Chem Int Ed Engl. 2017 Jun 12;56(25):7209-7212
pubmed: 28464551
Chem Commun (Camb). 2022 Jan 27;58(9):1318-1321
pubmed: 34950940
Angew Chem Int Ed Engl. 2003 Jan 13;42(2):151-3
pubmed: 12532343
J Am Chem Soc. 2021 Sep 1;143(34):13962-13970
pubmed: 34415748
Org Lett. 2020 Nov 6;22(21):8496-8499
pubmed: 33054232