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Synlett 2023; 34(20): 2443-2446
DOI: 10.1055/a-2091-0986
DOI: 10.1055/a-2091-0986
cluster
Special Issue Dedicated to Prof. Hisashi Yamamoto
Short Synthesis of a Biphenyl-Based Amino Triflamide Catalyst and Its Application in Enamine Catalysis
This work was supported by the Japan Society for the Promotion of Science (JSPS KAKENHI, Grant Numbers JP18H01975, JP22H02073, and JP20H04815) in Hybrid Catalysis.
![](https://www.thieme-connect.de/media/synlett/202320/lookinside/thumbnails/st-2023-u0137-l_10-1055_a-2091-0986-1.jpg)
This paper is dedicated to Professor Hisashi Yamamoto on the occasion of his 80th birthday.
Abstract
A novel axially chiral biphenyl-based amino triflamide has been designed and successfully synthesized from 1-nitropyrene in 6 steps. This chiral amino triflamide functions as effective catalyst for asymmetric Mannich reaction through enamine intermediates.
Key words
axial chirality - biphenyl - amine organocatalyst - enamine catalysis - Mannich reaction - aminoxylationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2091-0986.
- Supporting Information
Publication History
Received: 31 March 2023
Accepted after revision: 10 May 2023
Accepted Manuscript online:
10 May 2023
Article published online:
26 June 2023
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- 16 Typical Procedure for the Catalytic Asymmetric Mannich Reaction of N-PMP-Protected α-Iminoacetate 9 To a stirred solution of (S)-4 (0.9 mg, 0.0025 mmol) in dioxane (2.5 mL) were added an aldehyde (0.75 mmol) and ethyl (4-methoxyphenylimino)acetate 9 (48.9 μL, 0.25 mmol) in this order at room temperature. After being stirred at the same temperature, the reaction mixture was then quenched with a saturated aqueous NH4Cl solution and extracted with ethyl acetate. The combined organic extracts were dried over Na2SO4, filtered, and concentrated. The residue was purified by flash column chromatography on silica gel (hexane/ethyl acetate = 8:1 to 4:1) to give the corresponding Mannich adduct 10. Ethyl (2S,3R)-3-Formyl-2-(p-methoxyphenylamino)heptanoate (10a) Following the typical procedure, using hexanal (91.6 μL, 0.75 mmol) for 4 h gave the crude product. Purification by flash column chromatography gave the title compound (67 mg, 0.22 mmol, 87% yield, dr = 12:1, 91% ee). 1H NMR (500 MHz, CDCl3): δ = 9.65 (d, J = 2.5 Hz, 1 H), 6.80–6.76 (m, 2 H), 6.67–6.63 (m, 2 H), 4.26 (d, J = 6.0 Hz, 1 H), 4.18 (qd, J = 7.1, 3.0 Hz, 2 H), 3.74 (s, 3 H), 2.78–2.71 (m, 1 H), 1.79–1.68 (m, 1 H), 1.67–1.50 (m, 2 H), 1.44–1.28 (m, 3 H), 1.22 (t, J = 7.3 Hz, 3 H), 0.89 (t, J = 7.0 Hz, 3 H). HPLC analysis: Daicel CHIRALPAK IC-3, hexane/i-PrOH (19:1), 1.0 mL/min, λ = 254 nm, t major = 28.5 min, t minor = 39.0 min.
For pioneering works in enamine catalysis, see:
For reviews, see:
A similar biphenyl-based amine catalyst has also been developed, see: