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Synlett 2017; 28(09): 1096-1100
DOI: 10.1055/s-0036-1558952
DOI: 10.1055/s-0036-1558952
letter
Catalytic Enantioselective Aza-Piancatelli Rearrangement
Further Information
Publication History
Received: 01 December 2016
Accepted after revision: 20 January 2017
Publication Date:
13 February 2017 (online)
Abstract
The design and development of an enantioselective aza-Piancatelli rearrangement reaction are described. In the presence of a chiral phosphoric acid catalyst, furylcarbinols react with anilines to afford highly functionalized cyclopentenones with excellent diastereo- and enantioselectivities. The process was shown to be scalable, and up to 1 gram of starting material could be employed under mild reaction conditions.
Key words
aza-Piancatelli rearrangement - cyclopentenones - organocatalysis - furylcarbinols - anilines - asymmetric catalysisSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0036-1558952.
- Supporting Information
- CIF File
-
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- 11 (4R)-4-Anilino-5,5-diphenylcyclopent-2-en-1-one (3a); Typical Procedure A flame-dried screw-capped vial equipped with magnetic stirrer bar was charged with carbinol 1a (0.1 mmol, 1 equiv) and PhNH2 (2a; 0.12 mmol, 1.2 equiv). PhF (4 mL) was added at r.t., and the mixture was stirred for 10 min. Chiral phosphoric acid catalyst 4g (0.005 mmol, 5 mol%) was added under flowing N2. The reaction vial was fitted with a cap, and the mixture was stirred at 50 °C for 20 h. When conversion of the starting material was complete (TLC), the mixture was filtered through a plug of Celite, and the filtrate was concentrated. The residue was purified by column chromatography (silica gel, PE–EtOAc) to give an analytically pure white solid; yield: 27.3 mg (84%); mp 137–138 °C; Rf = 0.32 (PE–EtOAc, 9:1); [α]D 25 –192.45 (c = 1.18, CHCl3). 1H NMR (500 MHz, CDCl3): δ = 7.76 (br s, 1 H), 7.60–7.42 (m, 2 H), 7.32 (br s, 2 H), 7.22 (br s, 3 H), 7.10 (br s, 2 H), 6.99 (br s, 2 H), 6.69 (br s, 1 H), 6.44 (br. s, 3 H), 5.54 (d, J = 8.0 Hz, 1 H), 3.40–3.17 (m, 1 H). 13C NMR (125 MHz, CDCl3): δ = 206.9, 161.8, 145.8, 140.7, 140.5, 133.7, 129.7, 129.4, 128.5, 128.4, 128.2, 127.4, 127.3, 118.3, 113.4, 64.9, 63.4. HRMS (ESI): m/z [M + H]+ calcd for C23H20NO: 326.1539; found: 326.1538. HPLC: Chiralpak IB (80:20 hexane–i-PrOH), flow rate: 1.0 mL/min; λ = 254 nm; t R = 8.2 min (major), 9.0 min (minor); er = 97:3.
For reviews, see:
For selected references, see:
For a review, see:
For reports on the Piancatelli rearrangement, see:
For reports on aza-Piancatelli rearrangement, see:
For reactions triggered by the chiral phosphoric acid-catalyzed dehydration, see:
For reviews on BINOL-based Brønsted acid catalysis, see:
For reviews on asymmetric electrocyclic reactions, see:
For recent reports on chiral phosphoric acid-catalyzed Nazarov cyclization reactions, see:
For reports from our laboratory on chiral phosphoric acid catalysis, see: