Recently, our group and other researchers have demonstrated that hydrogen atom transfer (HAT) photocatalysis offers a promising avenue for achieving mild activation conditions in the functionalization of volatile alkanes. Although this reaction has historically posed practical challenges when conducted in batch conditions, the emergence of flow technology has introduced a convenient reactor platform. This reactor design enhances the overall irradiation profile within the reaction mixture and increases gas-liquid mass transfer rates. As a result, this approach leads to substantial reductions in reaction times, increased selectivity, and enhanced practicality for exploring a wider scope of reactions. Notwithstanding this recent progress, there are still significant limitations in the scope of available reactions suitable for light alkane activation. Sulfones, sulfonamides, and sulfonate esters represent ubiquitous functional groups with applications spanning various fields, including pharmaceuticals, agrochemicals, and material science (Figure ). Commonly, sulfinate salts serve as versatile precursors for constructing sulfur-containing compounds due to their reactivity and stability. Industrial methods currently employed for synthesizing sodium sulfinates rely on a two-step process involving the reduction of corresponding sulfonyl chlorides. These chlorides, in turn, are derived from the respective alkanes, sulfur dioxide (SO2), and chlorine gas (Figure ). This conventional approach necessitates the handling of highly hazardous and corrosive gases (SO2 and Cl2) at elevated temperatures and pressures. In light of the increasing use of sulfur dioxide and its surrogates in recent methodologies, our objective was to develop a method that harnesses the advantages of both flow chemistry and photocatalysis in conjunction with gaseous alkanes. While alkyl sulfinates derived from C1-4 alkanes are commonly found in drug structures (Figure ), their direct synthesis from light alkanes has proven to be an elusive task thus far. As presented herein, we have developed a general flow-based platform for generating synthetically valuable alkyl sulfinates directly from readily available and cost-effective gases (Figure ). Most notably, we demonstrated their synthetic utility in the late-stage functionalization of medicinally relevant organic scaffolds. We initiated our investigation into the proposed C(sp 3 )-H sulfinylation of gaseous alkanes by blending a mixture of propane and an aqueous solution of sulfur dioxide in the presence of tetrabutylammonium decatungstate (TBADT) in an acetonitrile:H2O solution (4:1, 0.2 M). This reaction mixture was then passed through a transparent continuous-flow microreactor (FEP tubing, ID=0.5 mm, 1.5 mL volume) exposed to six high-intensity UV-A light sources (Chipon-Board LED, λ = 365 nm, 144 W optical power). Subsequently, the reaction stream was combined with benzyl bromide and sodium bicarbonate using a fed-batch approach. To facilitate complete liquefaction of the gas and enhance the efficiency of C(sp )-H bond activation through decatungstate-catalysed HAT , a 34 bar back-pressure regulator (BPR) was positioned at the reactor outlet. After a careful exploration of various reaction conditions, we successfully obtained the desired product in a 48% yield, with just a one-hour residence time, in the presence of 1 mol% of TBADT (Table , Entries 1-2). Prolonged exposure to irradiation did not yield further improvements in the reaction yield likely due to degradation (Table , Entry 1). Increasing the amount of propane gas beyond 5 equivalents did not lead to a significant improvement in yield (Table , Entry 3). Remarkably, the choice of cation for the decatungstate photocatalyst was found to impact the reaction yield, with sodium decatungstate (NaDT) yielding a 59% yield, likely due to its higher solubility (Table , Entry 4). Higher concentrations of SO2 led to enhanced yields by improving reaction rates, simultaneously increasing the overall throughput and thus the scalability of the process (Table , Entry 5).