Abstract
Exocyclic allene natural products and pharmaceutical agents are rare but interesting compounds: Fucoxanthin, grasshopper ketone, and analogues of prostacyclins, cephalosporins, antithrombic agents and sterol biosynthesis inhibitors are representative. Syntheses of exocyclic allenes commonly rely on extended conjugate additions to e.g., alk-2-en-4-ynones, syn SN2′-like additions to alkynyl oxiranes, and substitution reactions such as electrophilic substitutions of propargylic silanes. We report that the reaction of 3-alkynyl-2-cycloalkenones with 2 equiv of various hydridoaluminates but not hydridoborates proceeds via diastereoselective 1,4-reduction of a vinylogously propargylic intermediate alcoholate to provide exocyclic allenes as major products. Isomeric 3-alkynylcycloalkanols also are observed.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 6052-6063 |
| Number of pages | 12 |
| Journal | Tetrahedron |
| Volume | 72 |
| Issue number | 40 |
| DOIs | |
| State | Published - Oct 6 2016 |
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All Science Journal Classification (ASJC) codes
- Biochemistry
- Drug Discovery
- Organic Chemistry
Cite this
Stereoselective synthesis of exocyclic allenes by double hydride reduction of 3-alkynyl-2-cycloalkenones. / Gubbels, Matthew A.; Hulce, Martin; Kum, John M.; Urick, Andrew K.; Villa, Eric.
In: Tetrahedron, Vol. 72, No. 40, 06.10.2016, p. 6052-6063.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Stereoselective synthesis of exocyclic allenes by double hydride reduction of 3-alkynyl-2-cycloalkenones
AU - Gubbels, Matthew A.
AU - Hulce, Martin
AU - Kum, John M.
AU - Urick, Andrew K.
AU - Villa, Eric
PY - 2016/10/6
Y1 - 2016/10/6
N2 - Exocyclic allene natural products and pharmaceutical agents are rare but interesting compounds: Fucoxanthin, grasshopper ketone, and analogues of prostacyclins, cephalosporins, antithrombic agents and sterol biosynthesis inhibitors are representative. Syntheses of exocyclic allenes commonly rely on extended conjugate additions to e.g., alk-2-en-4-ynones, syn SN2′-like additions to alkynyl oxiranes, and substitution reactions such as electrophilic substitutions of propargylic silanes. We report that the reaction of 3-alkynyl-2-cycloalkenones with 2 equiv of various hydridoaluminates but not hydridoborates proceeds via diastereoselective 1,4-reduction of a vinylogously propargylic intermediate alcoholate to provide exocyclic allenes as major products. Isomeric 3-alkynylcycloalkanols also are observed.
AB - Exocyclic allene natural products and pharmaceutical agents are rare but interesting compounds: Fucoxanthin, grasshopper ketone, and analogues of prostacyclins, cephalosporins, antithrombic agents and sterol biosynthesis inhibitors are representative. Syntheses of exocyclic allenes commonly rely on extended conjugate additions to e.g., alk-2-en-4-ynones, syn SN2′-like additions to alkynyl oxiranes, and substitution reactions such as electrophilic substitutions of propargylic silanes. We report that the reaction of 3-alkynyl-2-cycloalkenones with 2 equiv of various hydridoaluminates but not hydridoborates proceeds via diastereoselective 1,4-reduction of a vinylogously propargylic intermediate alcoholate to provide exocyclic allenes as major products. Isomeric 3-alkynylcycloalkanols also are observed.
UR - http://www.scopus.com/inward/record.url?scp=84986308331&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84986308331&partnerID=8YFLogxK
U2 - 10.1016/j.tet.2016.07.058
DO - 10.1016/j.tet.2016.07.058
M3 - Article
AN - SCOPUS:84986308331
VL - 72
SP - 6052
EP - 6063
JO - Tetrahedron
JF - Tetrahedron
SN - 0040-4020
IS - 40
ER -