The synthetic efficacy of β-chloroketones derived from vinyl arenes and phenylacetylenes is well documented in the literature. Selecting some representative examples, such transformations can also be carried out efficiently starting from 1 and 4 to obtain dihydropyrazole 102 and β-chloro alcohol 103 (Fig. and). In addition, we envisioned that the library of βchloroketones available in our arsenal could be further used as pluripotent intermediates for skeletal diversification. NaH mediated dehydrochlorination of 103 provided exclusively homoallylic alcohol 104 as a single diastereomer, while the formation of oxetane 105 that could arise via intramolecular nucleophilic displacement was not observed (Fig. ). Taking advantage of this synthetic pathway, alkene diol 106 was synthesized starting from 8 in 77% yield, which was transformed to the linear hydrocarbon phenyldodecane (107) following mesyl protection and hydrogenation (Fig. ). The reductionelimination sequence of cyclic β-chloroketone 30 led to the formation of oxabicyclo[3.2.0]heptane derivative 108 possibly via intramolecular Michaeladdition of intermediate VII (Fig. ). Moreover, we demonstrated that this strategy could be utilized in the construction of pyrrolodinone derivative 109 in 88% yield by NaH mediated cyclization of 14 (Fig. ). 2-Phenyltoluene (110) was also efficiently synthesized via intramolecular McMurry couplingdehydrochlorination-aromatization cascade of chloroketone 10 (Fig. ). Furthermore, 3-chloropropiophenone 111, a key synthetic intermediate to access (R)/(S)-Fluxeotine, tomoxetine and nisoxetine, could be obtained by exposing 24 to potassium tert-butoxide in DMSO (Fig. ). Epoxy-alcohol 112 was obtained by a desilylative cyclization followed by conversion to 1,3diol 113 using reported methods which is a valuable building block for the synthesis of fesoteridone, dapoxetine, atomoxetine, ezetimibe 61 (Fig. ).