Notably, ortho-substituents (products 20, 23, 24, 32) and even a free aniline (32) could be enlisted without diminishing the e.s.. The haloselectivity of the coupling, enabling the selective crosscoupling in the presence of reactive 2-chloro groups (18, 30, 33) is also notable for potential downstream diversification. Although most of the products of Table (16 out of 23) were never reported before, not even in racemic form, the majority are prophetically claimed within the Markush structures of several patents. Seven compounds (18, 19, 24, 25, 28, 31 and 34) were previously synthesized exclusively in racemic form using methods like Suzuki-hydrogenation, photochemical coupling, and reductive coupling from bromides. For example, the patented compound 18 was synthesized via Suzuki cross-coupling and hydrogenation using PtO2 as catalyst, followed by chiral SFC separation. Structure 34 was previously procured via reductive coupling from aryl and alkyl-bromides followed by chiral HPLC separation. alcohols and were found to be stable, crystalline solids. Tetrahydrofuran-and tetrahydropyranderived sulfonylhydrazides could be prepared either via a Mitsunobu reaction of the corresponding alcohols or amination of the amines by using O-(p-nitrobenzoyl)hydroxylamine. In the latter case, amination was preferable due to the lower cost of the corresponding enantiopure amine. For the sulfonylhydrazides leading to acyclic substrates, a simple SN2 reaction with hydrazine followed by tosylation was employed. In terms of limitations for the current conditions, the yields are generally moderate (ca. 50%), with the majority of the mass balance consisting of recovered aryl halide and alkane/alkene byproducts from decomposition of the sulfonylhydrazide. Currently, benzylic systems do not perform well (7% e.s., compound S34) presumably due to the faster racemization of such systems. The unusual solvent (carveol) employed in Condition B can often be replaced by the achiral protic solvent, cyclohexanol, thereby implicating solvent viscosity rather than solvent chirality as being a key trait for optimized stereoretention (for instance substrate 37 performed similarly (89.0 : 11.0 e.r., 80% e.s.), using cyclohexanol in place of carveol). In this initial report all optimization studies were focused on improving stereoretention and future studies will be focused on yield enhancement. It is worth mentioning that the current yields are similar to that observed in canonical, non stereoretentive radical cross coupling chemistry (vide infra). Tf, trifluoromethanesulfonyl.