AbstractFour putative functionalized α‐chloroakyllithiums RCH2CHLiCl, where R=CHCH2 (18 a), CCH (18 b), CH2OBn (18 c), and CH[O(CH2)2O] (18 d), were generated in situ by sulfoxide–lithium exchange from α‐chlorosulfoxides, and investigated for the stereospecific reagent‐controlled homologation (StReCH) of phenethyl and 2‐chloropyrid‐5‐yl (17) pinacol boronic esters. Deuterium labeling experiments revealed that α‐chloroalkyllithiums are quenched by proton transfer from their α‐chlorosulfoxide precursors and it was established that this effect compromises the yield of StReCH reactions. Use of α‐deuterated α‐chlorosulfoxides was discovered to ameliorate the problem by retarding the rate of acid‐base chemistry between the carbenoid and its precursor. Carbenoids 18 a and 18 b showed poor StReCH efficacy, particularly the propargyl group bearing carbenoid 18 b, the instability of which was attributed to a facile 1,2‐hydride shift. By contrast, 18 d, a carbenoid that benefits from a stabilizing interaction between O and Li atoms gave good StReCH yields. Boronate 17 was chain extended by carbenoids 18 a, 18 b, and 18 d in 16, 0, and 68 % yield, respectively; α‐deuterated isotopomers D‐18 a and D‐18 d gave yields of 33 and 79 % for the same reaction. Double StReCH of 17 was pursued to target contiguous stereodiads appropriate for the total synthesis of (−)‐epibatidine (15). One‐pot double StReCH of boronate 17 by two exposures to (S)‐D‐18 a (≤66 % ee), followed by work‐up with KOOH, gave the expected stereodiad product in 16 % yield (d.r.∼67:33). The comparable reaction using two exposures to (S)‐D‐18 d (≤90 % ee) delivered the expected bisacetal containing stereodiad (R,R)‐DD‐48 in 40 % yield (≥98 % ee, d.r.=85:15). Double StReCH of 17 using (S)‐D‐18 d (≤90 % ee) followed by (R)‐D‐18 d (≤90 % ee) likewise gave (R,S)‐DD‐48 in 49 % yield (≥97 % ee, d.r.=79:21). (R,S)‐DD‐48 was converted to a dideuterated isotopomer of a synthetic intermediate in Corey’s synthesis of 15.