Spirooxindoles are important synthetic targets possessing extended biological activity and drug discovery applications. This review focuses on the various strategies for the enantioselective synthesis of spirocyclic oxindoles relying on reports over the past decade and from earlier work. The spirooxindoles in this review are separated into three structural classes, and then further categorized into the method type from which the spirocycle is generated.

Deazaflavins are well suited for reductive chemistry acting via a consecutive photo‐induced electron transfer, in which their triplet state and semiquinone – the latter is formed from the former after electron transfer from a sacrificial electron donor – are key intermediates. Guided by mechanistic investigations aiming to increase intersystem crossing by the internal heavy atom effect and optimising the concentration conditions to avoid unproductive excited singlet reactions, we synthesised 5‐aryldeazaflavins with Br or Cl substituents on different structural positions via a three‐component reaction. Bromination of the deazaisoalloxazine core leads to almost 100 % triplet yield but causes photo‐instability and enhances unproductive side reactions. Bromine on the 5‐phenyl group in ortho position does not affect the photostability, increases the triplet yield, and allows its efficient usage in the photocatalytic dehalogenation of bromo‐ and chloroarenes with electron‐donating methoxy and alkyl groups even under aerobic conditions. Reductive powers comparable to lithium are achieved.

The regioselective three-component condensation of azomethine ylides derived from isatins and α-amino acids with acrylamides or aroylacrylic acids as dipolarophiles has been realized through a one-pot 1,3-dipolar cycloaddition protocol. Decarboxylation of 2'-aroyl-2-oxo-1,1',2,2',5',6',7',7a'-octahydrospiro[indole-3,3'-pyrrolizine]-1'-carboxylic acids is accompanied by cyclative rearrangement with formation of dihydropyrrolizinyl indolones.117

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