This discrepancy in sensitivity to substrate once again highlights the potential mechanistic differences between the (Z)and (E)-selective protocols (vide infra). Notably, the stereoconvergent methodology was not restricted to Suzuki-Miyaura couplings but was also successfully demonstrated under Ni-catalyzed Kumada-and Negishi cross-coupling conditions. Accordingly, a reaction with cyclopropylzinc bromide (2i) as the nucleophilic coupling partner generated the desired product 3ai with conservation of the ring system and high selectivity (82:18 dr) for the (E)-isomer as well as 87% yield. Under the Kumada cross-coupling regime, the methylated product 3aj was afforded with a high level of stereoconvergence (79:21 E/Z) and a yield of 70% using MeMgBr (2j) with L1. The reaction with L2 showed promising levels of convergence (67:33 E/Z) as well, but was lower yielding and did not produce the desired opposite diastereomer. We also probed the synthetic versatility of a diastereodivergent approach, which would generate tetrasubstituted alkene products (Z)-3 or (E)-3 selectively from diastereomerically enriched enol tosylates 1 (Scheme 3). Thus, several stereochemically defined (Z)-enol tosylates (Z)-1 were evaluated using a divergent protocol with the same (Z)-or (E)-selective reaction conditions C1 or C2, respectively, as employed for the diastereoconvergent approach. Generally, both product diastereomers were obtained in high diastereomeric ratios of up to 99:1 Z/E and 93:7 E/Z and typically good isolated yields of up to 92%. It is notable that some of the selectivities were higher than under convergent conditions, such as for product (Z)-3aa (97:3 versus 86:14 Z/E, cf. Scheme 1). In particular, the drop in (Z)-selectivity by variation in the northwestern quadrant (3aa vs 3ca) was not observed under the divergent conditions (cf. Scheme 1). Instead, the isopropyl-substituted product 3ca was isolated with a selectivity of 91:9 Z/E, albeit in moderate yield of 25%. The observation that the configuration of the enol tosylate starting material could have a profound effect on selectivity of the tetrasubstituted alkene product was further investigated by probing the corresponding isomeric tosylates (E)-1a under both conditions C1 and C2. With (E)-1a as the starting material, a lower ratio of 79:21 Z/E for 3aa was observed under the (Z)-selective conditions C1, whereas almost the same selectivity of 86:14 E/Z 3aa was obtained under (E)-selective conditions C2. The observation of the same product selectivity irrespective of the starting material geometry may indicate that a Curtin-Hammett scenario is likely operative under the (E)-selective reaction regime. In contrast, the product selectivity in the reaction under conditions C1 is more dependent on the enol tosylate geometry, indicating a different mechanistic manifold could be effective under these conditions (vide infra, Table ).