Haloarenes, cross-coupling of
Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
-Radical addition reactions of organyl iodides 7a-s onto [1.1.1]propellane (2) followed by halogen-lithium exchange and transmetallation with zinc chloride, as well as additions of Grignard reagents to 2, have furnished a variety of 3-substituted bicyclo[1.1.1]pentyl-1-magnesium (14) and -zinc (19) derivatives. The latter have been coupled with various alkenyl, aryl, and biaryl halides and triflates under NiCl2dppe, Pd(PPh3)4, or PdCl2(dppf) catalysis to give a number of 1,3-disubstituted bicyclo[1.1.1]pentyl derivatives 17, 20, and 23, several of which exhibit liquid crystalline properties, in moderate to very good yields. The coupling products 20ca, 23ab, 23ae, 23ff, and 23fg have been further transformed to yield bicyclo[1.1.1]pentyl derivatives 32, 24ab, 24ae, 27ff, and 27fg, respectively, bearing alkynyl, cyano, and/or alkenyl groups.
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