Via an X-ray analysis, the sulfonamide bearing R
1 =
i-Pr, R
2 = Me, and R
3 = Me is shown to be a tridentate ligand to a Cr(III) salt. This classof ligands, represented by R
1 =
t-Bu, R
2 = 2-naphthyl, and R
3 = Me, is effective to achieve an asymmetric Ni/Cr-mediated coupling reactionand, with the C14-C38 segment of halichondrins, its synthetic potential has been demonstrated. A possible mechanism is suggested for theprocess.