Abstract
Addition of cyanoformates (NC-COOR) to norbornene at 110 °C in the presence of Pd(PPh3)4 (10 mol %) as a catalyst affords with high selectivity the corresponding doubly functionalized polar norbornane derivatives bearing both cyano and ester groups. By using benzonorbornadiene and norbornadienes as the substrates, the reaction can be extended to synthesis of various functionalized norbornene derivatives in moderate to excellent yields. In most cases alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, and benzyl in the ester functionalities are applicable to the reactions. Oxidative addition of cyanoformates to Pd(0), insertion of norbornenes, and reductive elimination of the corresponding adducts constitute the proposed catalysis pathway.
| Original language | English |
|---|---|
| Pages (from-to) | 9872-9882 |
| Number of pages | 11 |
| Journal | Tetrahedron |
| Volume | 62 |
| Issue number | 42 |
| DOIs | |
| Publication status | Published - Oct 16 2006 |
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ASJC Scopus subject areas
- Biochemistry
- Organic Chemistry
- Drug Discovery
Cite this
Cyanoesterification of norbornenes catalyzed by palladium : facile synthetic methodology to introduce cyano and ester functionalities via direct carbon-carbon bond cleavage of cyanoformates. / Nishihara, Yasushi; Inoue, Yoshiaki; Izawa, Seisuke; Miyasaka, Mitsuru; Tanemura, Kenki; Nakajima, Kiyohiko; Takagi, Kentaro.
In: Tetrahedron, Vol. 62, No. 42, 16.10.2006, p. 9872-9882.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Cyanoesterification of norbornenes catalyzed by palladium
T2 - facile synthetic methodology to introduce cyano and ester functionalities via direct carbon-carbon bond cleavage of cyanoformates
AU - Nishihara, Yasushi
AU - Inoue, Yoshiaki
AU - Izawa, Seisuke
AU - Miyasaka, Mitsuru
AU - Tanemura, Kenki
AU - Nakajima, Kiyohiko
AU - Takagi, Kentaro
PY - 2006/10/16
Y1 - 2006/10/16
N2 - Addition of cyanoformates (NC-COOR) to norbornene at 110 °C in the presence of Pd(PPh3)4 (10 mol %) as a catalyst affords with high selectivity the corresponding doubly functionalized polar norbornane derivatives bearing both cyano and ester groups. By using benzonorbornadiene and norbornadienes as the substrates, the reaction can be extended to synthesis of various functionalized norbornene derivatives in moderate to excellent yields. In most cases alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, and benzyl in the ester functionalities are applicable to the reactions. Oxidative addition of cyanoformates to Pd(0), insertion of norbornenes, and reductive elimination of the corresponding adducts constitute the proposed catalysis pathway.
AB - Addition of cyanoformates (NC-COOR) to norbornene at 110 °C in the presence of Pd(PPh3)4 (10 mol %) as a catalyst affords with high selectivity the corresponding doubly functionalized polar norbornane derivatives bearing both cyano and ester groups. By using benzonorbornadiene and norbornadienes as the substrates, the reaction can be extended to synthesis of various functionalized norbornene derivatives in moderate to excellent yields. In most cases alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, and benzyl in the ester functionalities are applicable to the reactions. Oxidative addition of cyanoformates to Pd(0), insertion of norbornenes, and reductive elimination of the corresponding adducts constitute the proposed catalysis pathway.
UR - http://www.scopus.com/inward/record.url?scp=33748298869&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33748298869&partnerID=8YFLogxK
U2 - 10.1016/j.tet.2006.08.025
DO - 10.1016/j.tet.2006.08.025
M3 - Article
AN - SCOPUS:33748298869
VL - 62
SP - 9872
EP - 9882
JO - Tetrahedron
JF - Tetrahedron
SN - 0040-4020
IS - 42
ER -