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Synlett 2012(5): 741-746  
DOI: 10.1055/s-0031-1290358
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

2-(Diphenylphosphino)benzoyl-Substituted Calix[4]arene: Efficient Organocatalyst in Aza-Morita-Baylis-Hillman Reaction of N-Sulfonated Imines with Methyl Vinyl Ketone

Yanyan Shen, Qian Tang, Chenchen Zhang, Weihui Zhong*
Key Laboratory of Pharmaceutical Engineering of Ministry of Education, College of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 310014, P. R. of China
Fax: +86(571)88871087; e-Mail: weihuizhong@zjut.edu.cn;
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Publication History

Received 16 October 2011
Publication Date:
24 February 2012 (online)

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Abstract

A novel bifunctional organocatalyst 5,11,17,23-tetra­butyl-25-[2-(diphenylphosphino)benzoate]-26,27,28-trihydroxycalix-[4]arene (LB3) was synthesized and applied to promote the aza-Morita-Baylis-Hillman (aza-MBH) reaction of N-sulfonated im­ines with methyl vinyl ketone. It was found that in the presence of acidic additives the reaction rate could be accelerated to give aza-MBH adducts in good to excellent yields. Compared to our previous phosphine-containing calix[4]arene LB1, the novel catalyst was more effective.

Key word

phosphine-containing calix[4]arene - organocatalysis - aza-Morita-Baylis-Hillman

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9

Typical Procedure for the Preparation of LB3: A suspension of para-tert-butylcalix[4]arene (1.30 g, 2.0 mmol) in toluene (45 mL) was cooled to 0 ˚C. Then 2-(diphenylphosphino)benzoic acid (0.92 g, 3.0 mmol), dicyclohexylcarbodiimide (DCC, 0.699 g, 3.4 mmol) and 4-(N,N-dimethylamino)pyridine (DMAP; 0.041 g, 0.34 mmol) were added. After stirring at 60 ˚C for 12 h, the suspension was filtrated and extracted with CH2Cl2 (100 mL) and then washed with H2O (2 × 50 mL). The organic layer was dried with anhyd Na2SO4 and evaporated to afford a white solid that was purified by flash chromatography (EtOAc-PE, 1:30) to afford LB3; yield 60%; mp 181.0-182.1 ˚C. ¹H NMR (400 MHz, CDCl3): δ = 0.88 (s, 15 H, Me), 1.08 (s, 15 H, Me), 1.25 (s, 6 H, Me), 3.72 (m, 8 H, CH2), 6.10 (br, 1 H, OH), 6.49 (br, 2 H, OH), 6.68 (s, 2 H, ArH), 6.88 (s, 1 H, ArH), 7.01 (s, 1 H, ArH), 7.08 (s, 2 H, ArH), 7.17-7.23 (m, 6 H, ArH), 7.29 (t, J = 5.6 Hz, 9 H, ArH), 7.66 (s, 1 H, ArH). ¹³C NMR (100 MHz, CDCl3): δ = 162.1, 148.5, 148.1, 144.0, 143.1, 140.9, 140.6, 138.0, 137.9, 137.6, 137.5, 134.1 (2 × C), 133.9, 133.8, 133.5, 133.4, 132.9 (2 × C), 131.9 (2 × C), 131.6 (2 × C), 131.0, 130.8, 128.4 (2 × C), 128.3 (3 × C), 128.2 (4 × C), 126.8 (2 × C), 126.1 (2 × C), 125.9, 125.7, 125.3, 124.9, 124.8, 34.0, 33.9, 31.6 (9 × C), 31.3 (2 × C), 31.2 (2 × C), 31.1 (4 × C), 29.8. MS (ESI): m/z = 936.6 [M - 1]-. HRMS (ESI): m/z [M - 1]- calcd for C63H69O5P: 936.4883; found: 935.4756.

10

Typical Procedure for the Aza-Morita-Baylis-Hillman Reaction of N-Sulfonated Imines 1 with MVK in the Presence of LB3 (10 mol%): To N-(2-fluorobenzylidene)-4-methylbenzenesulfonamide (1a; 0.259 g, 1.0 mmol), LB3 (0.094 g, 0.10 mmol) and PhCO2H (0.012 g, 0.10 mmol) in CH2Cl2 (3.0 mL) was added MVK (0.105 g, 1.5 mmol) at r.t. Then the temperature was raised to 40 ˚C with stirring for 4 h. The solution was extracted with CH2Cl2 (20 mL) and then washed with H2O (2 × 15 mL). The organic layer was dried with Na2SO4 and evaporated to afford a white solid that was purified by flash chromatography (eluent: EtOAc-PE, 1:4) to give the corresponding aza-Morita-Baylis-Hillman adduct 3a (0.289 g, 88%); mp 120.2-121.3 ˚C (lit.,³g 120-121 ˚C). ¹H NMR (400 MHz, CDCl3): δ = 2.15 (s, 3 H, Me), 2.42 (s, 3 H, Me), 5.27 (d, J = 8.7 Hz, 1 H, CH2), 5.71 (d, J = 8.7 Hz, 1 H, CH2), 6.07 (s, 1 H, CH), 6.09 (s, 1 H, NH), 7.08 (m, 2 H, ArH), 7.17-7.22 (m, 5 H, ArH), 7.64 (d, J = 8.0 Hz, 2 H, ArH). MS (ESI): m/z = 328.2 [M - 1]-.