DFT studies of mechanism and origin of stereoselectivity of palladium-catalyzed cyclotrimerization reactions affording syn-tris(norborneno) benzenes

Masahiro Yamanaka, Masumi Morishima, Yukihiro Shibata, Shuhei Higashibayashi, Hidehiro Sakurai

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Pd-catalyzed cyclotrimerization reactions of enantiopure halonorbornene derivatives furnished C3 or C3v symmetric syn-tris(norborneno)benzenes with high syn selectivity. To elucidate the reaction mechanism as well as the stereoselectivity of the present Pd-catalyzed cyclotrimerization, DFT calculations were carried out. The promising reaction pathway consists of (1) sequential olefin insertion followed by an HX elimination reaction of halonorbornene with the norbornenylpalladium intermediate, (2) electrocyclization of the trienylpalladium intermediate with a lower activation barrier than a triene compound, and (3) the β-elimination of HPdX of the cyclohexadienylpalladium intermediate. In addition, the stereoselectivity would be controlled by the regioselectivity in the olefin insertion process (homo and hetero positions) and the symmetry breaking in the palladacyclic intermediate.

Original languageEnglish
Pages (from-to)3060-3068
Number of pages9
JournalOrganometallics
Volume33
Issue number12
DOIs
Publication statusPublished - 2014 Jun 23
Externally publishedYes

Fingerprint

Stereoselectivity
Palladium
Alkenes
Benzene
Discrete Fourier transforms
palladium
benzene
Regioselectivity
alkenes
insertion
elimination
Chemical activation
trienes
Derivatives
broken symmetry
selectivity
activation

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

DFT studies of mechanism and origin of stereoselectivity of palladium-catalyzed cyclotrimerization reactions affording syn-tris(norborneno) benzenes. / Yamanaka, Masahiro; Morishima, Masumi; Shibata, Yukihiro; Higashibayashi, Shuhei; Sakurai, Hidehiro.

In: Organometallics, Vol. 33, No. 12, 23.06.2014, p. 3060-3068.

Research output: Contribution to journalArticle

Yamanaka, Masahiro ; Morishima, Masumi ; Shibata, Yukihiro ; Higashibayashi, Shuhei ; Sakurai, Hidehiro. / DFT studies of mechanism and origin of stereoselectivity of palladium-catalyzed cyclotrimerization reactions affording syn-tris(norborneno) benzenes. In: Organometallics. 2014 ; Vol. 33, No. 12. pp. 3060-3068.
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