Samarium diiodide induced cyclizations of γ-, δ- and ε-indolyl ketones: reductive coupling, intermolecular trapping, and subsequent transformations of indolines.

Beemelmanns C, Lentz D, Reissig HU (2011) Samarium diiodide induced cyclizations of γ-, δ- and ε-indolyl ketones: reductive coupling, intermolecular trapping, and subsequent transformations of indolines. Chemistry 17(35), 9720-9730. PubMed

Abstract

This comprehensive study describes our results of samarium diiodide induced 5-exo-trig to 8-exo-trig cyclization/alkylation sequences of 3'-acceptor-substituted indolyl ketones. All cyclization precursors were easily prepared by simple N-alkylation or N-acylation of indole derivatives with the corresponding iodo alkanones, acid chlorides, or lactones. After treatment of indolyl ketones with two equivalents of SmI(2), the generated stabilized carbanionic intermediates were trapped with different electrophiles leading to a variety of highly substituted indoline derivatives in good to very good yields. In general, the cyclization products were obtained as single diastereomers bearing a newly generated quaternary center, a common structural motif in various indole alkaloids. The relative configurations of the products were established by NOE experiments and by single-crystal analysis and follow the rules already established. Furthermore, the obtained products were subjected to a series of chemical transformations, such as oxidation, reduction, and metathesis reactions resulting in a range of interesting synthetic building blocks valuable for further applications.

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doi: 10.1002/chem.201100981 PMID: 21744405