Stanger, Amnon; Ashkenazi, Nissan; Shachter, Alona; Blaeser, Dieter; Stellberg, Peter; Boese, Roland:

Nickel-Mediated Cyclobutabenzene Syntheses. trans-7,8-Dibromocyclobutabenzenes:Their One Pot Preparation, X-ray Structure and Diels-Alder Reactions.

In: Journal of Organic Chemistry (J.Org.Chem.), Jg. 61 (1996) ; Nr. 7, S. 2549-2552
ISSN: 0022-3263
Zeitschriftenaufsatz / Fach: Chemie
Abstract:
The use of nickel(0) complexes, [(1,2,3,4-h)-anthracene]bis(tributylphosphine)nickel, [(1,2,5,6-h)-1,5-cyclooctadiene]bis(tributylphosphine)nickel or metallic nickel to produce high yields of trans-7,8-dibromocyclobutabenzene (i.e., trans-7,8-dibromobicyclo[4.2.0]octa-1,3,5-triene) from a,a,a',a'-tetrabromo-o-xylene was reported. Trans-7,8-dibromobicyclo[4.2.0]octa-1,3,5-triene was characterized by x-ray crystallog., that confirmed the trans arrangement between the two bromine atoms. The cyclization reaction was also applied to substituted bis(bromomethyl)benzenes to yield the resp. trans-7,8-dibromocyclobutabenzenes. The reactions of trans-7,8-dibromocyclobutabenzenes with various dienophiles showed that the opening of the four membered ring of the cyclobutabenzenes is exclusively conrotatory (to produce the corresponding E,E-dibromo-o-xylylene), and that the addn. of the dienophile is exclusively endo. The reactions of trans-7,8-dibromobicyclo[4.2.0]octa-1,3,5-triene with unsym. substituted dienophiles yielded only one regioisomer.