A highly regio- and stereoselective nickel-catalyzed ring-opening reaction of alkyl- and allylzirconium reagents to 7-oxabenzonorbornadienes

Ming-Si Wu; Masilamani Jeganmohan; Chien-Hong Cheng

doi:10.1021/jo051660v

A highly regio- and stereoselective nickel-catalyzed ring-opening reaction of alkyl- and allylzirconium reagents to 7-oxabenzonorbornadienes

J Org Chem. 2005 Nov 11;70(23):9545-50. doi: 10.1021/jo051660v.

Authors

Ming-Si Wu¹, Masilamani Jeganmohan, Chien-Hong Cheng

Affiliation

¹ Department of Chemistry, Tsing Hua University, Hsinchu, Taiwan 30013.

PMID: 16268631
DOI: 10.1021/jo051660v

Abstract

[Reaction: see text]. An efficient method for the synthesis of cis-2-alkyl- or allyl-1,2-dihydronaphthalenes via a nickel-catalyzed highly regio- and stereoselective ring-opening addition of alkyl- or allylzirconium reagents to 7-oxabenzonorbornadienes is described. Treatment of 7-oxabenzonorbornadienes 1a-c with various alkylzirconium reagents 2a-j (Cp2ZrClCH2CH2R: R = tert-butyl, n-butyl, n-pentyl, -(CH2)3CH=C(CH3)2, -SiMe3, -CH2SiMe3, -(CH2)3Br, cyclopentyl, cyclohexyl, and benzyl) in the presence of NiBr2(dppe) and Zn powder in dry THF at 50 degrees C afforded the corresponding cis-2-alkyl-1,2-dihydronaphthalene derivatives 3a-m in good yields. In addition, allyl zirconium reagents 4a-c also underwent ring-opening reactions with 1a and 1c to give 5a-d in very good yields. The alkylative ring-opening products from 7-oxabenzonorbornadiene can be further converted to naphthalene derivatives 6a-c, via an acid-mediated dehydration, in good to excellent yields. A possible mechanism for the present catalytic reaction was proposed.