NDLI: Polar Diels–Alder reaction of isoprene toward 2-bromocyclobutenone followed by a subsequent sodium hydroxide-assisted ring contraction reaction. A regio- and stereoselectivity and molecular mechanism study using DFT

Content Provider	Royal Society of Chemistry (RSC)
Author	Emamian, Saeedreza
Copyright Year	2015
Abstract	The polar Diels–Alder (P-DA) reaction of isoprene, diene D10, toward 2-bromocyclobutenone, dienophile Dph4, in the presence of chloroform was theoretically studied using DFT methods at the MPWB1K/6-311G(d,p) level. Calculated relative Gibbs free energies associated with the four feasible reactive channels indicate that this P-DA cycloaddition takes place via C1–C5 regioselectivity and in a moderately endo-stereoselective manner, furnishing a formal [4+2] endo cycloadduct CA1n in excellent agreement with experimental outcomes. In the considered P-DA reaction, while C1–C5 regioselectivity can be explained using calculated Parr functions at the interacting sites of reagents, the moderately endo stereoselectivity is related to the favorable electrostatic interaction that appears in the endo-zwitterionic transition state TS1n as a consequence of the global electron density transfer (GEDT) that takes place during this polar reaction. In addition, the presence of the bulky bromine atom on Dph4 can destabilize the exoTS1x, acting as another important factor in the predominance of the endo stereoisomeric channel over the exo one. An electron localization function (ELF) topological analysis of the bonding changes during the investigated P-DA reaction supports a non-concerted, two-stage, one-step molecular mechanism in which the formation of a second C4–C6 single bond takes place after the almost complete formation of the first C1–C5 one. Moreover, the subsequent sodium hydroxide-assisted ring contraction reaction in the presence of acetonitrile converts generated CA1n into the final product, carane13, via a stepwise Favorskii process.
Starting Page	9525
Ending Page	9534
Page Count	10
File Format	HTM / HTML PDF
ISSN	11440546
Volume Number	39
Issue Number	12
Journal	New Journal of Chemistry
DOI	10.1039/c5nj01600b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Bromine Chloroform Regioselectivity Chemical bond Electron localization function Gibbs Diels\u2013Alder reaction Stereoselectivity Cycloaddition Parr Sodium Extremely low frequency Acetonitrile Topological data analysis Isoprene
Content Type	Text
Resource Type	Article
Subject	Chemistry Materials Chemistry Catalysis

Sl.	Authority	Responsibilities	Communication Details
1	Ministry of Education (GoI), Department of Higher Education	Sanctioning Authority	https://www.education.gov.in/ict-initiatives
2	Indian Institute of Technology Kharagpur	Host Institute of the Project: The host institute of the project is responsible for providing infrastructure support and hosting the project	https://www.iitkgp.ac.in
3	National Digital Library of India Office, Indian Institute of Technology Kharagpur	The administrative and infrastructural headquarters of the project	Dr. B. Sutradhar bsutra@ndl.gov.in
4	Project PI / Joint PI	Principal Investigator and Joint Principal Investigators of the project	Dr. B. Sutradhar bsutra@ndl.gov.in Prof. Saswat Chakrabarti will be added soon
5	Website/Portal (Helpdesk)	Queries regarding NDLI and its services	support@ndl.gov.in
6	Contents and Copyright Issues	Queries related to content curation and copyright issues	content@ndl.gov.in
7	National Digital Library of India Club (NDLI Club)	Queries related to NDLI Club formation, support, user awareness program, seminar/symposium, collaboration, social media, promotion, and outreach	clubsupport@ndl.gov.in
8	Digital Preservation Centre (DPC)	Assistance with digitizing and archiving copyright-free printed books	dpc@ndl.gov.in
9	IDR Setup or Support	Queries related to establishment and support of Institutional Digital Repository (IDR) and IDR workshops	idr@ndl.gov.in

Preparation and biological evaluation of novel leucomycin analogs derived from nitroso Diels–Alder reactions

Intramolecular Diels–Alder chemistry of 4-vinylimidazoles

Theoretical Study on Regioselectivity of the Diels-Alder Reaction between 1,8-Dichloroanthracene and Acrolein

On the Brassard's rule of regioselectivity in Diels–Alder reactions between haloquinones and polar dienes

Control of regioselectivity in the Diels–Alder reactions of alkyl-substituted 1,4-benzoquinones by β-cyclodextrin and its derivatives

Kinetics and regioselectivity in the Diels–Alder reaction of fulleroids vs. methanofullerene and C₆₀

Stereo- and regioselectivity of the hetero-Diels–Alder reaction of nitroso derivatives with conjugated dienes

Intramoléculaire Diels-Alder de Triène-Amide [ Theoretical Examination of the Stereoselectivity of the Intramolecular Cycloaddition Diels-Alder Reaction of Triene-Amide]

Chromium photocatalysis: accessing structural complements to Diels–Alder adducts with electron-deficient dienophiles

Polar Diels–Alder reaction of isoprene toward 2-bromocyclobutenone followed by a subsequent sodium hydroxide-assisted ring contraction reaction. A regio- and stereoselectivity and molecular mechanism study using DFT

Similar Documents

Preparation and biological evaluation of novel leucomycin analogs derived from nitroso Diels–Alder reactions

Intramolecular Diels–Alder chemistry of 4-vinylimidazoles

Theoretical Study on Regioselectivity of the Diels-Alder Reaction between 1,8-Dichloroanthracene and Acrolein

On the Brassard's rule of regioselectivity in Diels–Alder reactions between haloquinones and polar dienes

Control of regioselectivity in the Diels–Alder reactions of alkyl-substituted 1,4-benzoquinones by β-cyclodextrin and its derivatives

Kinetics and regioselectivity in the Diels–Alder reaction of fulleroids vs. methanofullerene and C60

Stereo- and regioselectivity of the hetero-Diels–Alder reaction of nitroso derivatives with conjugated dienes

Intramoléculaire Diels-Alder de Triène-Amide [ Theoretical Examination of the Stereoselectivity of the Intramolecular Cycloaddition Diels-Alder Reaction of Triene-Amide]

Chromium photocatalysis: accessing structural complements to Diels–Alder adducts with electron-deficient dienophiles

Polar Diels–Alder reaction of isoprene toward 2-bromocyclobutenone followed by a subsequent sodium hydroxide-assisted ring contraction reaction. A regio- and stereoselectivity and molecular mechanism study using DFT

Kinetics and regioselectivity in the Diels–Alder reaction of fulleroids vs. methanofullerene and C₆₀