Abstract
A convenient one-pot asymmetric synthesis of 2,3-dihydropyrroles from in situ generated triflated triazoles and olefins is described that further expands the utility of azavinyl carbene chemistry and provides access to an important class of cyclic enamides. Mechanistic investigations support the involvement of triflated cyclopropylaldimine intermediates in the formation of 2,3-dihydropyrrole. To the best of our knowledge, this is the first example of a chiral Brønsted acid catalyzed rearrangement of cyclopropylimines into enantioenriched 2,3-dihydropyrroles. Enantioenriched dihydropyrroles can be generated by a rhodium(II)-catalyzed asymmetric transannulation between sulfonyl-1,2,3-triazoles and electron-rich styrenes. Mechanistic investigations support the formation of cyclopropane intermediates which undergo ring expansion to 2,3-dihydropyrroles in the presence of a chiral Brønsted acid catalyst.
| Original language | English |
|---|---|
| Pages (from-to) | 3452-3456 |
| Number of pages | 5 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 53 |
| Issue number | 13 |
| DOIs | |
| Publication status | Published - 24 Mar 2014 |
| Externally published | Yes |
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Keywords
- azavinyl carbenes
- dihydropyrroles
- enamides
- rhodium
- triazoles
ASJC Scopus subject areas
- Chemistry(all)
- Catalysis
- Medicine(all)
Cite this
Catalytic asymmetric transannulation of NH-1,2,3-triazoles with olefins. / Kwok, Sen Wai; Zhang, Li; Grimster, Neil P.; Fokin, Valery V.
In: Angewandte Chemie - International Edition, Vol. 53, No. 13, 24.03.2014, p. 3452-3456.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Catalytic asymmetric transannulation of NH-1,2,3-triazoles with olefins
AU - Kwok, Sen Wai
AU - Zhang, Li
AU - Grimster, Neil P.
AU - Fokin, Valery V.
PY - 2014/3/24
Y1 - 2014/3/24
N2 - A convenient one-pot asymmetric synthesis of 2,3-dihydropyrroles from in situ generated triflated triazoles and olefins is described that further expands the utility of azavinyl carbene chemistry and provides access to an important class of cyclic enamides. Mechanistic investigations support the involvement of triflated cyclopropylaldimine intermediates in the formation of 2,3-dihydropyrrole. To the best of our knowledge, this is the first example of a chiral Brønsted acid catalyzed rearrangement of cyclopropylimines into enantioenriched 2,3-dihydropyrroles. Enantioenriched dihydropyrroles can be generated by a rhodium(II)-catalyzed asymmetric transannulation between sulfonyl-1,2,3-triazoles and electron-rich styrenes. Mechanistic investigations support the formation of cyclopropane intermediates which undergo ring expansion to 2,3-dihydropyrroles in the presence of a chiral Brønsted acid catalyst.
AB - A convenient one-pot asymmetric synthesis of 2,3-dihydropyrroles from in situ generated triflated triazoles and olefins is described that further expands the utility of azavinyl carbene chemistry and provides access to an important class of cyclic enamides. Mechanistic investigations support the involvement of triflated cyclopropylaldimine intermediates in the formation of 2,3-dihydropyrrole. To the best of our knowledge, this is the first example of a chiral Brønsted acid catalyzed rearrangement of cyclopropylimines into enantioenriched 2,3-dihydropyrroles. Enantioenriched dihydropyrroles can be generated by a rhodium(II)-catalyzed asymmetric transannulation between sulfonyl-1,2,3-triazoles and electron-rich styrenes. Mechanistic investigations support the formation of cyclopropane intermediates which undergo ring expansion to 2,3-dihydropyrroles in the presence of a chiral Brønsted acid catalyst.
KW - azavinyl carbenes
KW - dihydropyrroles
KW - enamides
KW - rhodium
KW - triazoles
UR - http://www.scopus.com/inward/record.url?scp=84896483388&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84896483388&partnerID=8YFLogxK
U2 - 10.1002/anie.201306706
DO - 10.1002/anie.201306706
M3 - Article
VL - 53
SP - 3452
EP - 3456
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 13
ER -