Abstract
The gold(I)-catalyzed cyclization of the cyclohexa-1,3-diene bearing a terminal alkyne and a gemdiester in the tether proceeds via a cationic gold intermediate to give a tetrahydromethyleneindene derivative. Changing the gem-diester to a gem-diketone in the tether, the transient gold-stabilized carbocation is trapped intramolecularly by a methyl ketone to afford a tricyclo[5.4.04,8]undecane ring skeleton. Under the same reaction conditions, aryl-substituted cyclohexadienynes afford hexahydroacephenanthrylene rings in a diastereoselective fashion and in good yields. The reaction proceeded via attack of the aryl group onto the gold-stabilized carbocations followed by aromatization and protodemetalation to generate the tetracarbocycles. This cycloaddition can be applied to the synthesis of pentahydronapthoazulenes from aryl-substituted cycloheptadienynes and the gold(I) catalyst.
| Original language | English |
|---|---|
| Pages (from-to) | 5326-5332 |
| Number of pages | 7 |
| Journal | Organometallics |
| Volume | 27 |
| Issue number | 20 |
| DOIs | |
| Publication status | Published - 2008 Oct 27 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
Cite this
Facile synthesis of carbotetracycles via gold(i)-catalyzed cyclization of unactivated cyclic 1-aryl-6,8-dien-1-ynes. / Yeh, Ming Chang P.; Tsao, Wen Cheng; Lee, Bo Jen; Lin, Tzu G.
In: Organometallics, Vol. 27, No. 20, 27.10.2008, p. 5326-5332.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Facile synthesis of carbotetracycles via gold(i)-catalyzed cyclization of unactivated cyclic 1-aryl-6,8-dien-1-ynes
AU - Yeh, Ming Chang P.
AU - Tsao, Wen Cheng
AU - Lee, Bo Jen
AU - Lin, Tzu G.
PY - 2008/10/27
Y1 - 2008/10/27
N2 - The gold(I)-catalyzed cyclization of the cyclohexa-1,3-diene bearing a terminal alkyne and a gemdiester in the tether proceeds via a cationic gold intermediate to give a tetrahydromethyleneindene derivative. Changing the gem-diester to a gem-diketone in the tether, the transient gold-stabilized carbocation is trapped intramolecularly by a methyl ketone to afford a tricyclo[5.4.04,8]undecane ring skeleton. Under the same reaction conditions, aryl-substituted cyclohexadienynes afford hexahydroacephenanthrylene rings in a diastereoselective fashion and in good yields. The reaction proceeded via attack of the aryl group onto the gold-stabilized carbocations followed by aromatization and protodemetalation to generate the tetracarbocycles. This cycloaddition can be applied to the synthesis of pentahydronapthoazulenes from aryl-substituted cycloheptadienynes and the gold(I) catalyst.
AB - The gold(I)-catalyzed cyclization of the cyclohexa-1,3-diene bearing a terminal alkyne and a gemdiester in the tether proceeds via a cationic gold intermediate to give a tetrahydromethyleneindene derivative. Changing the gem-diester to a gem-diketone in the tether, the transient gold-stabilized carbocation is trapped intramolecularly by a methyl ketone to afford a tricyclo[5.4.04,8]undecane ring skeleton. Under the same reaction conditions, aryl-substituted cyclohexadienynes afford hexahydroacephenanthrylene rings in a diastereoselective fashion and in good yields. The reaction proceeded via attack of the aryl group onto the gold-stabilized carbocations followed by aromatization and protodemetalation to generate the tetracarbocycles. This cycloaddition can be applied to the synthesis of pentahydronapthoazulenes from aryl-substituted cycloheptadienynes and the gold(I) catalyst.
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UR - http://www.scopus.com/inward/citedby.url?scp=55249110856&partnerID=8YFLogxK
U2 - 10.1021/om8005917
DO - 10.1021/om8005917
M3 - Article
AN - SCOPUS:55249110856
VL - 27
SP - 5326
EP - 5332
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 20
ER -