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. 2021 May 5;12(25):8706-8712.
doi: 10.1039/d1sc01127h. eCollection 2021 Jul 1.

Catalytic (3 + 2) annulation of donor-acceptor aminocyclopropane monoesters and indoles

Vincent Pirenne  1 , Emma G L Robert  1 , Jerome Waser  1
Affiliations

Catalytic (3 + 2) annulation of donor-acceptor aminocyclopropane monoesters and indoles

Vincent Pirenne et al. Chem Sci. .

Abstract

The efficient catalytic activation of donor-acceptor aminocyclopropanes lacking the commonly used diester acceptor is reported here in a (3 + 2) dearomative annulation with indoles. Bench-stable tosyl-protected aminocyclopropyl esters were converted into cycloadducts in 46-95% yields and up to 95 : 5 diastereomeric ratio using catalytic amounts of triethylsilyl triflimide. Tricyclic indoline frameworks containing four stereogenic centers including all-carbon quaternary centers were obtained.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. D–A cyclopropanes with one or two acceptor groups in annulation reactions.
Scheme 2
Scheme 2. Annulations of D–A cyclopropanes and indoles.
Scheme 3
Scheme 3. Screening of several push–pull systems for the TMS triflimide-catalyzed (3 + 2) annulation of aminocyclopropanes 1a–f with 1-methylindole (2a).
Scheme 4
Scheme 4. Scope of the catalytic (3 + 2) annulation of tosyl-protected aminocyclopropane 1 with indoles 2 (reaction on 0.1 to 0.3 mmol scale, yields are given for the mixture of both isomers). aReaction performed at room temperature.
Scheme 5
Scheme 5. Scale up experiments and product modifications. Reaction conditions: (a) DIBALH, THF, 0 °C; (b) Li/naphthalene, THF, rt; (c) TBAF, THF, 0 °C.
Scheme 6
Scheme 6. Influence of the absolute and relative configuration of the starting aminocyclopropane 1d on the (3 + 2) annulation with 1-methylindole (2a) (a); speculative mechanism proposal (b).
See this image and copyright information in PMC

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