In nature, prenylation and geranylation are two important metabolic processes for the creation of hemiterpenoids and monoterpenoids under enzyme catalysis. Herein, we have demonstrated bioinspired unnatural prenylation and geranylation of oxindoles using the basic industrial feedstock isoprene through ligand regulation under Pd catalysis. Pentenylated oxindoles (with C 5 added) were attained with high selectivity when using a bisphosphine ligand, whereas upon switching to a monophosphine ligand, selectivity toward geranylated oxindoles (with C 10 added) was achieved. Moreover, the head-to-head product could be further isomerized to an internal skipped diene under PdÀ H catalysis. No stoichiometric by-product was formed in the process.

Thiophene-based rings are one of the most widely used building blocks for the synthesis of sulfur-containing molecules.I nspired by the redox diversity of these features in nature,w ed emonstrate herein ar edox-divergent construction of dihydrothiophenes,thiophenes,and bromothiophenes from the respective readily available allylic alcohols,d imethyl sulfoxide (DMSO), and HBr.T he redox-divergent selectivity could be manipulated mainly by controlling the dosage of DMSO and HBr.M echanistic studies suggest that DMSO simultaneously acts as an oxidant and as ulfur donor.T he synthetic potentials of the products as platform molecules were also demonstrated by various derivatizations,i ncluding the preparation of bioactive and functional molecules.