A Mn(OAc)3-Triggered Formation of Cyclopropanes from Ugi Adducts

Cristina Cheibas; Emilie Vieu; Nicolas Casaretto; Maxime Vitale; Laurence Grimaud; Laurent El Kaïm

doi:10.1055/a-2005-5220

Synlett, Inhaltsverzeichnis

Synlett 2023; 34(13): 1581-1586
DOI: 10.1055/a-2005-5220

letter

A Mn(OAc)₃-Triggered Formation of Cyclopropanes from Ugi Adducts

Cristina Cheibas

^aLaboratoire de Synthèse Organique (LSO -UMR 76523) CNRS, Ecole Polytechnique, ENSTA-Paris, Institut Polytechnique de Paris, 828 Bd des Maréchaux, 91128 Palaiseau Cedex, France

,

Emilie Vieu

^aLaboratoire de Synthèse Organique (LSO -UMR 76523) CNRS, Ecole Polytechnique, ENSTA-Paris, Institut Polytechnique de Paris, 828 Bd des Maréchaux, 91128 Palaiseau Cedex, France

,

Nicolas Casaretto

^bLaboratoire de Chimie Moléculaire (LCM -UMR 9168) CNRS, Ecole Polytechnique, Institut Polytechnique de Paris, 91128 Palaiseau Cedex, France

,

Maxime Vitale

^cLaboratoire des Biomolécules LBM, Département de Chimie, École Normale Supérieure, PSL University, Sorbonne Université, CNRS, 24 Rue Lhomond, 75005 Paris, France

,

Laurence Grimaud

^cLaboratoire des Biomolécules LBM, Département de Chimie, École Normale Supérieure, PSL University, Sorbonne Université, CNRS, 24 Rue Lhomond, 75005 Paris, France

,

Laurent El Kaïm ∗

^aLaboratoire de Synthèse Organique (LSO -UMR 76523) CNRS, Ecole Polytechnique, ENSTA-Paris, Institut Polytechnique de Paris, 828 Bd des Maréchaux, 91128 Palaiseau Cedex, France

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Abstract

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Abstract

Ugi adducts involving malonic acid monoesters and dialkoxy-substituted aromatic aldehydes can undergo an oxidative dearomatization when treated with Mn(OAc)₃ leading to the formation of fused cyclopropanes as observed in the Buchner reaction of diazo compounds.

Key words

manganese acetate - Ugi reaction - radical cyclization - cyclopropanation

Volltext

Referenzen

References and Notes
1 New address: Direction ISAE, ISAE-SUPAERO - 10 Avenue Edouard Belin - BP 54032 - 31055 Toulouse Cedex 4, France.

2a Buchner E, Curtius T. Ber. Dtsch. Chem. Ges. 1885; 2377
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For reviews, see:

2c Maier G. Angew. Chem., Int. Ed. Engl. 1967; 6: 402
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First intramolecular Buchner reaction:

2f Scott LT. J. Chem. Soc., Chem. Commun. 1973; 22: 882

For some Buchner reactions of anisole derivatives, see:

2g Clarke AK, Unsworth WP, Taylor RJ. K. Tetrahedron 2018; 74: 5374

3a El Kaïm L, Grimaud L, Miranda LD, Vieu E.. Tetrahedron Lett. 2006; 47: 8259
3b El Kaïm L, Grimaud L, Vieu E. Org. Lett. 2007; 9: 4171
3c El Kaïm L, Grimaud L, Miranda LD, Vieu E, Cano-Herrera MA, Perez-Labrada K.. Chem. Commun. 2010; 46: 2489
3d Gamez-Montano R, Ibarra-Rivera T, El Kaïm L, Miranda LD. Synthesis 2010; 1285
3e El Kaïm L, Grimaud L, Le Goff X-F, Menes-Arzate M, Miranda LD. Chem. Commun. 2011; 47: 8145

For some reviews, see:

4a Snider BB. Chem. Rev. 1996; 96: 339
4b Mondal M, Bora U. RSC Adv. 2013; 3: 18716
4c Snider BB. In Manganese Catalysis in Organic Synthesis . Sortais JB. Wiley; London: 2021: 293

5 Marcaccini S, Pepino R, Cruz Pozo M, Basurto S, Garcıa-Valverde M, Torroba T. Tetrahedron Lett. 2004; 45: 3999
6 CCDC 2205405 contains the supplementary crystallographic data for compounds 2b. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
7 Typical Procedure for the Synthesis of Ugi Adducts To a solution of 2,3-dimethoxy-benzaldehyde (499 mg, 3.0 mmol, 1.0 equiv) in MeOH (3 mL) were added successively 2-methoxyethylamine (0.263 mL, 3.0 mmol, 1.0 equiv), malonic acid monoethyl ester (0.369 mL, 3.0 mmol, 1.0 equiv), and t-butyl isocyanide (0.341 mL, 3.0 mmol, 1.0 equiv). The resulting mixture was stirred at rt for 16 h. The solvent was removed under reduced pressure, and the crude product was purified by flash chromatography using (Et₂O:PE, 70:30 to 100:0) to afford the desired product 1a in 64% isolated yield (834 mg, 1.9 mmol) as white solid; mp 122–124 °C. R_f = 0.4 (Et₂O). ¹H NMR (400 MHz, CDCl₃, * = minor rotamer): δ = 7.16* (s, 1 H), 7.01–6.95 (m, 1 H, 2 H*), 6.90–6.86 (m, 1 H, 1 H*), 6.78 (dd, J _H–H = 7.7 Hz, J _H–H = 0.7 Hz, 1 H), 6.27 (s, 1 H), 6.13 (s, 1 H), 5.52* (s, 1 H), 4.19–4.11 (m, 2 H, 2 H*), 3.82–3.79 (m, 1 H), 3.82 (s, 3 H), 3.81* (s, 3 H), 3.80* (s, 3 H), 3.79 (s, 3 H), 3.68–3.62* (m, 1 H), 3.53–3.46 (m, 2 H, 2 H*), 3.41 (dd, J _H–H = 7.1 Hz, J _H–H = 4.9 Hz, 1 H), 3.38–3.34* (m, 1 H), 3.29–3.22* (m, 2 H), 3.25* (s, 3 H), 3.11 (s, 3 H), 3.07 (dd, J _H–H = 10.1 Hz, J _H–H = 4.9 Hz, 1 H), 2.81 (ddd, J _H–H = 10.1 Hz, J _H–H = 7.1 Hz, J _H–H = 4.9 Hz, 1 H), 1.37* (s, 9 H), 1.32 (s, 9 H), 1.23 (t, J _H–H = 7.1 Hz, 3 H, 3 H*). ¹³C NMR (100 MHz, CDCl₃, * = minor rotamer): δ = 168.7, 168.6, 168.5*, 168.4*, 167.7*, 167.6, 152.7, 152.4*, 148.2, 147.7*, 129.5, 128.6*, 124.0, 123.9*, 122.6, 120.9*, 113.3*, 112.9, 70.9, 69.5*, 62.4*, 61.4 (1 C, 1 C*), 60.5 (1 C, 1 C*), 58.9, 58.5*, 58.2, 55.8 (1 C, 1 C*), 51.6*, 51.4, 46.4, 45.2*, 41.9*, 41.5, 28.7 (3 C), 28.6* (3 C), 14.1 (1 C, 1 C*). HRMS: m/z calcd for C₂₂H₃₅N₂O₇ ⁺: 439.2439; found: 439.2424. IR (thin film): ν = 3335, 2952, 1746, 1656, 1477, 1307, 1273, 1231, 1045, 886, 752 cm^–1. General Procedure for the Conversion of 1a into 2a To a solution of Ugi adduct 1a (88 mg, 0.2 mmol, 1.0 equiv) in acetic acid (0.03 M) was added Mn(OAc)₃·2H₂O (276 mg, 1.0 mmol, 5.0 equiv) under argon, and the resulting solution was stirred at 90 °C for 5 h until the dark brown color of Mn(III) acetate had disappeared. The solvent was removed under reduced pressure, and the crude mixture was filtered on a small amount of silica gel to remove residues of Mn, then purified by flash chromatography (Et₂O:PE, 90:10 to 100:0) to afford the desired product 2a in 55% isolated yield (53 mg, 0.11 mmol) as yellow oil. R_f = 0.25 (Et₂O). ¹H NMR (400 MHz, CDCl₃): δ = 5.95 (dd, J _H–H = 6.1 Hz, J _H–H = 0.8 Hz, 1 H), 5.87 (s, 1 H), 5.55 (dd, J _H–H = 6.1 Hz, J _H–H = 1.7 Hz, 1 H), 5.07 (s, 1 H), 4.20–4.09 (m, 2 H), 3.81–3.75 (m, 1 H), 3.60–3.55 (m, 1 H), 3.59 (s, 3 H), 3.52–3.47 (m, 1 H), 3.33 (s, 3 H), 3.21 (ddd, J _H–H = 14.7 Hz, J _H–H = 8.8 Hz, J _H–H = 3.5 Hz, 1 H), 2.66 (t, J _H–H = 1.2 Hz, 1 H), 1.97 (s, 3 H), 1.32 (s, 9 H), 1.21 (t, J _H–H = 7.1 Hz, 3 H). ¹³C NMR (100.6 MHz, CDCl₃): δ = 185.7, 169.9, 166.8, 166.0, 162.4, 153.3, 106.8, 70.7, 63.4, 62.7, 58.8, 58.5, 55.7, 51.8, 47.2, 41.9, 41.0, 30.6, 28.7 (3 C), 20.9, 14.0. HRMS: m/z calcd for C₂₃H₃₂N₂O₉ ⁺: 481.2181; found: 481.2178. IR (thin film): ν = 3349, 2971, 1738, 1693, 1221, 1092 cm^–1.
8 The starting malonic amide was prepared by a selective amidification of the diester followed by saponification, see: Zidan A, Garrec J, Cordier El Naggar MA. M, El-Sattar NE. A, Ali AK, Hassan MA, El Kaïm L. Angew. Chem. Int. Ed. 2017; 56: 12179

9a Zidan A, El-Naggar AM, Abd El-Sattar NE. A, Khaloil Ali A, El Kaïm L. Front. Chem. 2019; 7: 20
9b Yan Y.-M, Wang M.-L, Liu Y.-L, He Y.-C. Tetrahedron 2020; 76: 131389
9c Polindara-Garcia LA, Miranda LD. Org. Lett. 2012; 14: 5408

10 El Kaïm L, Gamez-Montano R, Grimaud L, Ibarra-Rivera T. Chem. Commun. 2008; 1350

11a Shundo R, Nishiguchi I, Matsubara Y, Hirashima T. Tetrahedron 1991; 47: 831
11b Warsinsky R, Steckhan E. J. Chem. Soc., Perkin Trans. 1 1994; 2027
11c Strehl J, Hilt G. Org. Lett. 2019; 21: 5259

12 Cyclic voltammetry experiments did not allow detecting the enol form of 1a, even at 90 °C.

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