On the Ring-Opening Reaction of Thiophene-1,1-dioxides and the Intramolecular Diels-Alder Reaction of Azanona- and AzadecatrienesI
(1997)- Abstract
- Substituted thiophene-1,1-dioxides were synthesized and their ring-opening reactions with omega-unsaturated secondary amines were investigated; this led to a synthetic route to azatrienes and to the preparation of some polyhydroisoindoles and polyhydroisoquinolines via an intramolecular Diels-Alder reaction. By using 2-substituted pyrrolidines and piperidines various tetrahydrobenzo[f]indolizidines, benzo[b]quinolizidines, tetrahydrobenzo[a]indolizidines and tetrahydro[a]pyrrolizidines could be synthesized via the ring-opening of 3-bromo-2,5-dimmethylthiophene-1,1-dioxide and a subsequent intramolecular Diels-Alder reaction. Aminoalcohols such as L-prolinol worked well and a diastereo- selective synthesis of substituted... (More)
- Substituted thiophene-1,1-dioxides were synthesized and their ring-opening reactions with omega-unsaturated secondary amines were investigated; this led to a synthetic route to azatrienes and to the preparation of some polyhydroisoindoles and polyhydroisoquinolines via an intramolecular Diels-Alder reaction. By using 2-substituted pyrrolidines and piperidines various tetrahydrobenzo[f]indolizidines, benzo[b]quinolizidines, tetrahydrobenzo[a]indolizidines and tetrahydro[a]pyrrolizidines could be synthesized via the ring-opening of 3-bromo-2,5-dimmethylthiophene-1,1-dioxide and a subsequent intramolecular Diels-Alder reaction. Aminoalcohols such as L-prolinol worked well and a diastereo- selective synthesis of substituted tetrahydro[a]pyrrolizidines was achieved. Asymmetric induction was observed in the L-prolinol induced ring-opening of 3-bromo-5-ethyl-2-isopropylthiophene-1,1- dioxide. A multivariate optimization procedure involving the use of response surface methodologies was undertaken to improve yields in the ring-opening reaction of 2-alkyl-3-bromo-5-methylthiophene- 1,1-dioxides. The mechanism of the ring-opening reaction was studied by isotope labeling and measure- ments of kinetic isotope effects. Semiempirical and ab initio calculations were made on transition states in order to explain stereoselectivities of the intramolecular Diels-Alder reaction in the azanona- and aza- decatriene series. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/29517
- author
- Tsirk, Anders Sebastian LU
- supervisor
- opponent
-
- Docent Somfai, Peter, Organic Chemistry 2, P.O. Box 124, 221 00 Lund
- organization
- publishing date
- 1997
- type
- Thesis
- publication status
- published
- subject
- keywords
- transition states, 3-21G(*), intramolecular Diels-Alder reactions, asymmetric induction, multivariate optimization, kinetic isotope effects, rearrangements, secondary amines, 1-dioxides, Ring-opening reaction, thiophene-1, stereoselectivity., Organic chemistry, Organisk kemi
- pages
- 179 pages
- defense location
- lecture hall D, Chemical Center
- defense date
- 1997-09-26 10:15:00
- external identifiers
-
- other:ISRN: LUNDL/NKOK-1037-SE
- ISBN
- 91-628-2639-5
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Organic chemistry (S/LTH) (011001240)
- id
- f4dd8f5d-064c-46fd-af64-d820b73715cf (old id 29517)
- date added to LUP
- 2016-04-04 13:12:58
- date last changed
- 2018-11-21 21:12:44
@phdthesis{f4dd8f5d-064c-46fd-af64-d820b73715cf,
abstract = {{Substituted thiophene-1,1-dioxides were synthesized and their ring-opening reactions with omega-unsaturated secondary amines were investigated; this led to a synthetic route to azatrienes and to the preparation of some polyhydroisoindoles and polyhydroisoquinolines via an intramolecular Diels-Alder reaction. By using 2-substituted pyrrolidines and piperidines various tetrahydrobenzo[f]indolizidines, benzo[b]quinolizidines, tetrahydrobenzo[a]indolizidines and tetrahydro[a]pyrrolizidines could be synthesized via the ring-opening of 3-bromo-2,5-dimmethylthiophene-1,1-dioxide and a subsequent intramolecular Diels-Alder reaction. Aminoalcohols such as L-prolinol worked well and a diastereo- selective synthesis of substituted tetrahydro[a]pyrrolizidines was achieved. Asymmetric induction was observed in the L-prolinol induced ring-opening of 3-bromo-5-ethyl-2-isopropylthiophene-1,1- dioxide. A multivariate optimization procedure involving the use of response surface methodologies was undertaken to improve yields in the ring-opening reaction of 2-alkyl-3-bromo-5-methylthiophene- 1,1-dioxides. The mechanism of the ring-opening reaction was studied by isotope labeling and measure- ments of kinetic isotope effects. Semiempirical and ab initio calculations were made on transition states in order to explain stereoselectivities of the intramolecular Diels-Alder reaction in the azanona- and aza- decatriene series.}},
author = {{Tsirk, Anders Sebastian}},
isbn = {{91-628-2639-5}},
keywords = {{transition states; 3-21G(*); intramolecular Diels-Alder reactions; asymmetric induction; multivariate optimization; kinetic isotope effects; rearrangements; secondary amines; 1-dioxides; Ring-opening reaction; thiophene-1; stereoselectivity.; Organic chemistry; Organisk kemi}},
language = {{eng}},
school = {{Lund University}},
title = {{On the Ring-Opening Reaction of Thiophene-1,1-dioxides and the Intramolecular Diels-Alder Reaction of Azanona- and AzadecatrienesI}},
year = {{1997}},
}