Starting from the inexpensive 2,2-difluoro-1,3-benzodioxole or its 5-bromo deriv., two new atropisomeric bisphosphines have been prepd. which, after racemate resoln., exhibit attractive features as ligands for enantioselective catalysts. The key step in their synthesis is a low temp. Ullmann reaction. An improved protocol secures coupling yields of 70-80%. For example, the treatment of 5,5-dibromo-2,2,2',2'-tetrafluoro[4,4'-bi-1,3-benzodioxole] with diphenylphosphinous chloride gave (2,2,2',2'-tetrafluoro[4,4'-bi-1,3-benzodioxole]-5,5'-diyl)bis[diphenylphosphine] (I). The resoln. of I was not reported. The application of (+)-I and (-)-I was previously reported. [on SciFinder (R)]