Indole-ynones have been established as general substrates for radical dearomatizing spirocyclization cascade reactions. Five distinct and varied synthetic protocols have been developedcyanomethylation, sulfonylation, trifluoromethylation, stannylation and borylationusing a variety of radical generation modes, ranging from photoredox catalysis to traditional AIBN methods. The simple and easily prepared indole-ynones can be used to rapidly generate diverse, densely functionalized spirocycles and have the potential to become routinely used to explore radical reactivity. Experimental and computational investigations support the proposed radical cascade mechanism and suggest that other new methods are now primed for development.

An operationally simple, high yielding three-step cascade process is described for the direct conversion of indole-tethered ynones into functionalized quinolines. A single “multitasking” thiol reagent is used to promote a three-step dearomatizing spirocyclization, nucleophilic substitution, and one-atom ring expansion reaction cascade under remarkably mild conditions. In addition, a novel route to thio-oxindoles is described, which was discovered by serendipity.

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8-Aminoindolizidines were synthesized from L-asparagine as the chiral starting material. The key dibenzylamino succinimide intermediate was synthesized in two steps. Three homologs of chiral hydroxylactams tethered with hydroxyalkene were synthesized from the succinimide via a sequence involving N-alkylation, cross olefin metathesis and hydride reduction. The dibenzylamino group gave the stereocontrol of the key N-acyliminium ion cyclization of these hydroxylactams. 5-Substituted-aminoindolizidines were synthesized with high diastereoselectivity at C6. A tandem cyclization of N-(6-hydroxyhex-3-en-1-yl)-g-hydroxylactam resulted in formation of tetrahydrofurano[2,3-g]indolizidine system.