Superacid-Promoted Dual C–C Bond Formation by Friedel–Crafts Alkylation and Acylation of Ethyl Cinnamates: Synthesis of Indanones

Bokka Venkat Ramulu; Alavala Gopi Krishna Reddy; Gedu Satyanarayana

doi:10.1055/s-0032-1318405

Synlett, Inhaltsverzeichnis

Synlett 2013; 24(7): 868-872
DOI: 10.1055/s-0032-1318405

letter

Superacid-Promoted Dual C–C Bond Formation by Friedel–Crafts Alkylation and Acylation of Ethyl Cinnamates: Synthesis of Indanones

Authors

Bokka Venkat Ramulu

Indian Institute of Technology (IIT) Hyderabad, Ordnance Factory Estate Campus, Yeddumailaram 502 205, Medak District, Andhra Pradesh, India Fax: +91(40)23016032 eMail: gvsatya@iith.ac.in
Alavala Gopi Krishna Reddy

Indian Institute of Technology (IIT) Hyderabad, Ordnance Factory Estate Campus, Yeddumailaram 502 205, Medak District, Andhra Pradesh, India Fax: +91(40)23016032 eMail: gvsatya@iith.ac.in
Gedu Satyanarayana*

Indian Institute of Technology (IIT) Hyderabad, Ordnance Factory Estate Campus, Yeddumailaram 502 205, Medak District, Andhra Pradesh, India Fax: +91(40)23016032 eMail: gvsatya@iith.ac.in

Abstract

Alle Artikel dieser Rubrik

Dedicated to the memory of my mentor Prof. A. Srikrishna (1955–2013), an outstanding organic chemist and a constant source of inspiration.

Abstract

A superacid (triflic acid) promoted dual C–C bond formation via intermolecular Friedel–Crafts alkylation (Michael addition type) and intramolecular acylation for the efficient synthesis of 3-substituted indan-1-ones is presented. This method was successful in activating ethyl cinnamates towards dual aromatic electrophilic substitution. Moreover, it enabled us to synthesize novel spirotetracyclic systems.

Key words

cinnamates - indanones - Friedel–Crafts alkylation - acylation - superacid

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Referenzen

References and Notes
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15 General Procedure for Friedel–Crafts Alkylation and Acylation of Ethyl Cinnamates (GP-1)To an oven-dried Schlenk tube under nitrogen atmosphere were added ester 1 (100 mg, 0.42–0.57 mmol), arene 2 (in case of benzene, toluene, and xylene 12 equiv and for other electron-rich arenes 1.5 equiv were used for 1 equiv of ester 1) and DCE (2 mL), followed by the addition of TfOH [3 equiv (i.e., 1.26–1.71 mmol)]. The resultant reaction mixture was stirred at 80 °C for 12–24 h. Progress of the reaction was monitored by TLC until the reaction was completed. The reaction mixture was quenched by the addition of aq NaHCO₃ and extracted with CH₂Cl₂ (3 × 20 mL). The combined organic layers were washed with sat. NaCl solution, dried (Na₂SO₄), and concentrated under reduced pressure. Purification of the residue by silica gel column chromatography (PE–EtOAc) furnished the indanone 3 (54–92%).Representative Analytical DataCompound 3f: IR (MIR-ATR, 4000–600 cm^–1): 2966, 2930, 1710, 1602, 1491, 1462, 1288, 1234, 1151, 1093, 1012, 828, 762, 674, 582 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.78 (d, 1 H, J = 7.3 Hz, ArH), 7.60 (dd, 1 H, J = 7.8, 7.3 Hz, ArH), 7.43 (dd, 1 H, J = 7.8, 7.3 Hz, ArH), 7.25 (d, 1 H, J = 7.8 Hz, ArH), 7.24 (ddd, 2 H, J=8.8, 2.4, 2.4 Hz, ArH), 7.10 (ddd, 2 H, J = 8.8, 2.4, 2.4 Hz, ArH), 2.91 (d, 1 H, J = 19.1 Hz, CH_a H_bCO), 2.88 (d, 1 H, J = 19.1 Hz, CH_a H_b CO), 1.81 [s, 3 H, ArC(CH₂CO)CH ₃] ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 205.3 (s, C=O), 162.3 (s, ArC), 145.8 (s, ArC), 135.6 (s, ArC), 135.4 (d, ArCH), 132.3 (s, ArC), 128.5 (d, 2 C, ArCH), 128.0 (d, ArCH), 127.7 (d, 2 C, ArCH), 125.4 (d, ArCH), 123.4 (d, ArCH), 55.5 (t, CH₂CO), 45.6 [s, ArC(CH₂CO)CH₃], 28.3 [q, ArC(CH₂CO)CH₃] ppm. HRMS (APCI⁺): m/z calcd for [C₁₆H₁₄ClO]⁺: 257.0728 [M + H]⁺; found: 257.0724.Compound 3g: IR (MIR-ATR, 4000–600 cm^–1): 2964, 2851, 1705, 1581, 1488, 1399, 1282, 1244, 1160, 1093, 826, 724, 665, 588 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.57 (s, 1 H, ArH), 7.42 (d, 1 H, J = 7.8 Hz, ArH), 7.22 (ddd, 2 H, J = 8.8, 2.4, 2.4 Hz, ArH), 7.14 (d, 1 H, J = 7.8 Hz, ArH), 7.10 (ddd, 2 H, J = 8.8, 2.4, 2.4 Hz, ArH), 2.89 (d, 1 H, J = 19.1 Hz, CH_a H_bCO), 2.87 (d, 1 H, J = 19.1 Hz, CH_a H_b CO), 2.42 (s, 3 H, ArCH₃), 1.78 [s, 3 H, ArC(CH₂CO)CH₃] ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 205.4 (s, C=O), 159.7 (s, ArC), 146.1 (s, ArC), 138.0 (s, ArC), 136.6 (d, ArCH), 135.9 (s, ArC), 132.2 (s, ArC), 128.5 (d, 2 C, ArCH), 127.6 (d, 2 C, ArCH), 125.1 (d, ArCH), 123.3 (d, ArCH), 55.8 (t, CH₂CO), 45.3 [s, ArC(CH₂CO)CH₃], 28.3 [q, ArC(CH₂CO)CH₃], 21.1 (q, ArCH₃) ppm. HRMS (APCI⁺): m/z calcd for [C₁₇H₁₆ClO]⁺: 271.0884 [M + H]⁺; found: 271.0880.

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