Cyanoesterification of norbornenes catalyzed by palladium: facile synthetic methodology to introduce cyano and ester functionalities via direct carbon-carbon bond cleavage of cyanoformates

Yasushi Nishihara, Yoshiaki Inoue, Seisuke Izawa, Mitsuru Miyasaka, Kenki Tanemura, Kiyohiko Nakajima, Kentaro Takagi

Research output: Contribution to journalArticle

56 Citations (Scopus)

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 languageEnglish
Pages (from-to)9872-9882
Number of pages11
JournalTetrahedron
Volume62
Issue number42
DOIs
Publication statusPublished - Oct 16 2006

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Palladium
Norbornanes
Esters
Bearings (structural)
Carbon
Derivatives
Catalyst selectivity
Catalysis
Catalysts
Substrates
2-norbornene

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 journalArticle

Nishihara, Yasushi ; Inoue, Yoshiaki ; Izawa, Seisuke ; Miyasaka, Mitsuru ; Tanemura, Kenki ; Nakajima, Kiyohiko ; Takagi, Kentaro. / Cyanoesterification of norbornenes catalyzed by palladium : facile synthetic methodology to introduce cyano and ester functionalities via direct carbon-carbon bond cleavage of cyanoformates. In: Tetrahedron. 2006 ; Vol. 62, No. 42. pp. 9872-9882.
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AU - Tanemura, Kenki

AU - Nakajima, Kiyohiko

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