Details
| Original language | English |
|---|---|
| Pages (from-to) | 9257-9262 |
| Number of pages | 6 |
| Journal | Chemistry - A European Journal |
| Volume | 27 |
| Issue number | 36 |
| Early online date | 25 Apr 2021 |
| Publication status | Published - 25 Jun 2021 |
Abstract
The different reactivity of trienones under Lewis and Brønsted acids catalysis was investigated, resulting in distinct cyclization products and carbon backbones that originated either from a conjugate Prins cyclization or an interrupted Nazarov cyclization. In particular, an unprecedented Nazarov cyclization tandem reaction is presented, terminating the oxyallyl cation by an ene-type reaction, and leading stereoselectively to bicyclic spiro compounds. The terminal olefin of this motif represents a useful handle for further functionalization, making it a strategic intermediate in total syntheses. The tandem Nazarov/ene cyclization was shown to be preferred over a Nazarov/[3+2] tandem reaction for all our substrates, independent of chain length. Deuteration studies further support the mechanistic hypothesis of the terminating ene reaction.
Keywords
- cyclization, domino reactions, ene reaction, Nazarov cyclization, spiro compounds
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- Organic Chemistry
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In: Chemistry - A European Journal, Vol. 27, No. 36, 25.06.2021, p. 9257-9262.
Research output: Contribution to journal › Article › Research
}
TY - JOUR
T1 - A Nazarov‐Ene Tandem Reaction for the Stereoselective Construction of Spiro Compounds
AU - Kalesse, Markus
AU - Etling, Christoph
AU - Tedesco, Giada
N1 - Funding Information: We thank Dr. J. Fohrer, M. Rettstadt and D. K?rtje for detailed NMR analysis and Dr. G. Dr?ger, A. Schulz and R. Reichel for mass spectra. We thank A. Eggert, Y. Linne and L. Millbrodt for assisting in the preparation of the manuscript. C. E. thanks Dr. E. A. Stempel for support in the early stages of the project. Open access funding enabled and organized by Projekt DEAL.
PY - 2021/6/25
Y1 - 2021/6/25
N2 - The different reactivity of trienones under Lewis and Brønsted acids catalysis was investigated, resulting in distinct cyclization products and carbon backbones that originated either from a conjugate Prins cyclization or an interrupted Nazarov cyclization. In particular, an unprecedented Nazarov cyclization tandem reaction is presented, terminating the oxyallyl cation by an ene-type reaction, and leading stereoselectively to bicyclic spiro compounds. The terminal olefin of this motif represents a useful handle for further functionalization, making it a strategic intermediate in total syntheses. The tandem Nazarov/ene cyclization was shown to be preferred over a Nazarov/[3+2] tandem reaction for all our substrates, independent of chain length. Deuteration studies further support the mechanistic hypothesis of the terminating ene reaction.
AB - The different reactivity of trienones under Lewis and Brønsted acids catalysis was investigated, resulting in distinct cyclization products and carbon backbones that originated either from a conjugate Prins cyclization or an interrupted Nazarov cyclization. In particular, an unprecedented Nazarov cyclization tandem reaction is presented, terminating the oxyallyl cation by an ene-type reaction, and leading stereoselectively to bicyclic spiro compounds. The terminal olefin of this motif represents a useful handle for further functionalization, making it a strategic intermediate in total syntheses. The tandem Nazarov/ene cyclization was shown to be preferred over a Nazarov/[3+2] tandem reaction for all our substrates, independent of chain length. Deuteration studies further support the mechanistic hypothesis of the terminating ene reaction.
KW - cyclization
KW - domino reactions
KW - ene reaction
KW - Nazarov cyclization
KW - spiro compounds
UR - http://www.scopus.com/inward/record.url?scp=85106745902&partnerID=8YFLogxK
U2 - 10.1002/chem.202101041
DO - 10.1002/chem.202101041
M3 - Article
VL - 27
SP - 9257
EP - 9262
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 36
ER -