Indole Synthesis via Allenyl Ester; Enantioselective Total Synthesis of Geissoschizoline

Methyl indole‐2‐acetate is a key structural motif in plant‐derived indole alkaloids. In this study, a mild and efficient protocol is presented for its preparation using readily available aniline derivatives, which are synthesized from malonic esters. The reaction proceeds via an allenyl ester intermediate, with NaCN‐mediated indole formation occurring at ambient temperature, affording high yields and broad substrate scope. The synthetic utility of this approach is demonstrated through the asymmetric total synthesis of geissoschizoline, a Strychnos ‐type monoterpenoid indole alkaloid. This synthesis not only establishes a novel route to monoterpenoid indole alkaloids but also achieves complete stereochemical control in constructing the six chiral centers of the natural product.