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. 2017 Sep 25;56(40):12206-12209.
doi: 10.1002/anie.201706694. Epub 2017 Aug 23.

Enantioselective Tandem Cyclization of Alkyne-Tethered Indoles Using Cooperative Silver(I)/Chiral Phosphoric Acid Catalysis

Yugen Zhu  1 , Wei He  1 , Wei Wang  1 , Chloe E Pitsch  2 , Xiaotai Wang  2 , Xiang Wang  1
Affiliations

Enantioselective Tandem Cyclization of Alkyne-Tethered Indoles Using Cooperative Silver(I)/Chiral Phosphoric Acid Catalysis

Yugen Zhu et al. Angew Chem Int Ed Engl. .

Abstract

Reported is the enantioselective synthesis of tetracyclic indolines using silver(I)/chiral phosphoric acid catalysis. A variety of alkyne-tethered indoles are suitable for this process. Mechanistic studies suggest that the in situ generated silver(I) chiral phosphate activates both the alkyne and the indole nucleophile in the initial cyclization step through an intermolecular hydrogen bond and the phosphate anion promotes proton transfer. In addition, further modifications of the cyclization products enabled stereochemistry-function studies of a series of bioactive indolines.

Keywords: asymmetric catalysis; cyclization; density functional calculations; polycycles; silver.

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Figures

Figure 1
Figure 1
Representative natural and synthetic polycyclic indolines. a) Structures of representative natural indoline alkaloids. b) Our previous gold approach to diverse bioactive polycyclic indolines.
Figure 2
Figure 2
Density functional calculation results. a) Energy diagram of the first cyclization beginning with 6a. Numbers are free energies in kcal mol-1. b) Optimized structures of TS-I and TS-I’. Most H atoms are omitted for clarity. All inter-atomic distances are in Å. Tol=toluene.
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