Inducing high exo selectivity in Diels-Alder reaction by dimethylborane substituent: a DFT study.
Journal
Scientific reports
ISSN: 2045-2322
Titre abrégé: Sci Rep
Pays: England
ID NLM: 101563288
Informations de publication
Date de publication:
23 Dec 2022
23 Dec 2022
Historique:
received:
20
09
2022
accepted:
19
12
2022
entrez:
23
12
2022
pubmed:
24
12
2022
medline:
24
12
2022
Statut:
epublish
Résumé
In this work, the role of Lewis acid-base (LAB) interaction on the stereoselectivity of the Diels-Alder (DA) reaction has been studied by DFT in gas and solution (dichloromethane) phases. The calculations were performed at the B3LYP/6-311G++ (d, p) level. Two different series of DA reactions were investigated: (1)-three mono-substituted cyclopentadienes + dimethyl(vinyl)borane; (2)-five α,β-unsaturated carbonyl compounds + cyclopenta-2,4-dien-1-yldimethylborane. The reacting diene and dienophile pairs were chosen to restrict LAB interaction to the exo reaction pathway. It was found that in some of the examined cases, the favorable LAB interaction is so strong that it can lead to a completely exo-selective DA reaction. Furthermore, a novel multistep synthetic method was hypothesized for preparing exo cycloadduct with near 100% stereoselectivity. Our results can open up new avenues toward the rational design of exo-selective DA reactions for synthesizing novel bioorganic compounds.
Identifiants
pubmed: 36564456
doi: 10.1038/s41598-022-26685-y
pii: 10.1038/s41598-022-26685-y
pmc: PMC9789069
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
22225Informations de copyright
© 2022. The Author(s).
Références
J Org Chem. 2007 May 25;72(11):4220-7
pubmed: 17465571
J Am Chem Soc. 2012 Jun 27;134(25):10646-50
pubmed: 22656241
J Phys Chem A. 2008 Oct 9;112(40):9970-7
pubmed: 18785697
Phys Rev B Condens Matter. 1988 Jan 15;37(2):785-789
pubmed: 9944570
Chem Commun (Camb). 2022 Sep 20;58(75):10572-10575
pubmed: 36048133
Org Lett. 2015 Sep 18;17(18):4432-5
pubmed: 26351987
Org Lett. 2006 Jun 22;8(13):2795-8
pubmed: 16774259
Sci Rep. 2016 Oct 12;6:35147
pubmed: 27731360
Org Biomol Chem. 2011 Oct 7;9(19):6616-22
pubmed: 21842074
Org Lett. 2007 Jul 19;9(15):2859-62
pubmed: 17580885
J Comput Chem. 2003 Apr 30;24(6):669-81
pubmed: 12666158
Molecules. 2020 May 29;25(11):
pubmed: 32486033
J Org Chem. 2002 Dec 13;67(25):9080-2
pubmed: 12467433
J Org Chem. 2002 Jul 12;67(14):4715-21
pubmed: 12098280
Angew Chem Int Ed Engl. 2020 Apr 6;59(15):6201-6206
pubmed: 31944503
Angew Chem Int Ed Engl. 2003 Jul 14;42(27):3078-115
pubmed: 12866094
J Am Chem Soc. 2016 Feb 17;138(6):1877-83
pubmed: 26799581
J Phys Chem A. 2009 May 14;113(19):5718-22
pubmed: 19385638
Chemistry. 2019 Mar 15;25(16):4058-4061
pubmed: 30697832
J Phys Chem A. 2009 May 14;113(19):5806-12
pubmed: 19382751
Angew Chem Int Ed Engl. 2002 May 17;41(10):1668-98
pubmed: 19750686
J Org Chem. 2019 Apr 5;84(7):3940-3952
pubmed: 30865446
J Inorg Biochem. 2000 Apr;79(1-4):179-85
pubmed: 10830864
Org Lett. 2002 May 2;4(9):1543-6
pubmed: 11975624
Org Lett. 2000 Jun 29;2(13):1927-1929
pubmed: 10891193