Lithium alkenyl berates of general structure 5 (RT = alkenyl) couple with cis bromides 1 at room temperature overnight in the presence of NiCl2(PPh3)(2) as a catalyst to furnish dienes of general structure 3 with retention of the olefin geometries present in both coupling partners. By using this reaction, cis,trans dienes 3 (R = TBDMS, TES, TBDPS; R-1 = n-C5H11, c-C6H11; R-2 = H; R-3 = n-C5H11, Ph) and cis,cis diene 3 (R = TBDMS; R-1 = R-2 = n-C5H11; R-3 = H) are synthesized in good yields. (C) 1998 Elsevier Science Ltd. All rights reserved.