The diversity of products from this reaction could be enriched by varying the readily accessible (hetero)aryl sulfones (2) (Fig ). The electronic properties of substituents on benzothiazolyl group had little impact on the reaction outcomes, and products (5a-5e) were delivered in comparable yields. In addition, compounds with other heteroaryls such as benzoxazolyl (5f), benzofuryl (5g), benzothienyl (5h), thienyl (5i), thiazolyl (5j), and pyridyl (5k) could be incorporated into an alkyne, leading to the corresponding allylic alcohols in useful yields. Though the migration of aryl groups is much slower than that of heteroaryls and in fact failed on many occasions, cinnamyl alcohols (5l-5o) were readily obtained in this reaction via phenyl migration. Notably, the reaction with alkynyl or alkenyl substituted sulfones resulted in a conjugated 1,3-enynyl alcohol (5p) and a 1,3-dienyl alcohol (5q) as a result of alkynyl or alkenyl migration. The alkyl substituent of sulfones was subsequently examined and it was found that both linear and cyclic alkyl moieties such as cyclopentyl, cyclohexyl and piperidyl could be introduced to the alkyne, forming 1,1-dialkyl-substituted tertiary allylic alcohols (5r-5w). The method is applicable to the preparation of secondary allylic alcohols (5x-5ab), and notably, the valuable deuterium-labeled allylic alcohol (5ac) could be readily produced using the appropriate deuterated sulfone reagent. The products from this reaction could be employed as versatile intermediates, highlighting the synthetic value of the method (Fig ). The benzothiazolyl group in 3a serves as the precursor of carbonyl group, readily releasing a formyl and giving rise to the corresponding conjugated aldehyde in a useful yield. The dehydration of 3a resulted in the conformationally unified s-cis diene that could serve in Diels-Alder reaction. Treatment of 3a with diethylaminosulfur trifluoride (DAST) furnished the allylic fluoride , and with TMSN3 afforded allylic azide . The benzyl group in 3a was removed in the presence of Lewis acid, and the subsequent spontaneous cyclization led to a 2H-pyran . The epoxidation of alkenyl of 3a smoothly generated the multifunctionalized oxirane . with 2a furnished the ring-opened product , indicating that radical pathways were involved in the reaction which was initiated by homolysis the C-Br bond (2a) (Fig. ). The tautomerization of Z-3a to E-3a took place only in the presence of a photosensitizer under light irradiation. However, this process is irreversible and the conversion of E-3a to Z-3a failed in the presence or absence of a photosensitizer (Fig. ). The absorption peaks of Z-3a (325 nm) or E-3a (329 nm) did not overlap with the emission wavelength of green light (λmax = 510 nm), suggesting that the conversion of Z-to E-isomer was enabled by the energy transfer (EnT) from the excited photosensitizer to substrate rather than by the direct light excitation of substrate 46-49 . Light on-off experiments showed that the reaction proceeded under light irradiation and stopped in its absence (Fig. ). This result is consistent with the quantum yield of the reaction (Φ < 0.6 for details, see the SI), illustrating that the reaction is a light-dependent process. A Stern-Volmer analysis demonstrated that the luminescence emission of fac-Ir(ppy)3 was efficiently quenched by 2a but not by 1a (Fig. ). EPR experiments displayed a conspicuous response signal when 5,5dimethyl-1-pyrroline N-oxide (DMPO) was added to the reaction as a radical trap (Fig. ) 24 . A plausible mechanism for the reaction is shown in Fig. . A single-electron transfer from the excited fac-Ir(ppy)3 to 2a generates an alkyl radical (I) that adds to the alkyne (1a) to form an alkenyl radical species (II). This radical is rapidly captured by the heteroaryl moiety, triggering the functional group migration. The competitive alkenyl radical-mediated 1,5-HAT is less favorable, and this was supported by DFT calculations (Fig. ), and is not observed in the reaction. As is explicitly shown in Fig. , the 1,4-aryl migration proceeds with a lower energetic barrier than a 1,5-HAT (TS1 vs TS2), leading to a more stable intermediate (IV), as opposed to III. The ensuing extrusion of SO2 affords a radical (V) which is then single-electron oxidized by in-situ generated Ir IV species to form the cation (VI) and regenerating the ground-state Ir III catalyst. Subsequently, nucleophilic addition of H2O to VI generates Z-3a. With the aid of photosensitizer, the energy transfer causes the conversion of Z-3a to the final product (E-3a) under light irradiation.