Advanced
Synthesis of Poly-Substituted Benzene Derivatives via [3+3] Annulation Protocol from Morita-Baylis-Hillman Adducts and Glutaconates
Synthesis of Poly-Substituted Benzene Derivatives via [3+3] Annulation Protocol from Morita-Baylis-Hillman Adducts and Glutaconates
Bulletin of the Korean Chemical Society. 2013. Nov, 34(11): 3503-3506
Copyright © 2013, Korea Chemical Society
  • Received : August 14, 2013
  • Accepted : August 30, 2013
  • Published : November 20, 2013
Download
PDF
e-PUB
PubReader
PPT
Export by style
Article
Author
Metrics
Cited by
TagCloud
About the Authors
Jin Woo Lim
Se Hee Kim
Jin Yu
Jae Nyoung Kim

Abstract
Keywords
PPT Slide
Lager Image
PPT Slide
Lager Image
PPT Slide
Lager Image
PPT Slide
Lager Image
PPT Slide
Lager Image
Experimental Section
The starting materials MBH bromides were prepared according to the reported method from MBH adducts with aqueous HBr or PBr 3 . 11 Glutaconate derivatives 2a ( E ) and 2b ( E ) were prepared by esterification of commercial trans -glutaconic acid. Triethyl aconitate ( 2c , E ) was prepared by esterification of commercial trans -aconitic acid. 12
Typical Synthetic Procedure of 3a. A stirred solution of 1a (239 mg, 1.0 mmol), 2a (205 mg, 1.1 mmol), Cs 2 CO 3 (489 mg, 1.5 mmol) in DMF (3.0 mL) was heated to 90 ℃ for 1 h. After the usual aqueous extractive workup and column chromatographic purification process (hexane/ether, 10:1), compound 3a 2a was obtained as colorless oil, 235 mg (72%). Other compounds were synthesized similarly, and the spectroscopic data of 3b-i and 4a are as follows.
Compound 3b: 70%; white solid, mp 52-54 ℃; IR (KBr) 1719, 1434, 1322, 1233 cm −1 ; 1 H NMR (CDCl 3 , 300 MHz) δ 2.39 (s, 3H), 3.82 (s, 3H), 3.83 (s, 3H), 4.02 (s, 2H), 6.98- 7.02 (m, 2H), 7.08-7.23 (m, 3H), 7.90 (d, J = 1.8 Hz, 1H), 8.28 (d, J = 1.8 Hz, 1H); 13 C NMR (CDCl 3 , 75 MHz) δ 16.98, 39.78, 52.16, 52.18, 126.27, 127.43, 128.41, 128.54, 129.62, 131.87, 134.11, 139.14, 140.77, 143.37, 166.37, 168.09; ESIMS m/z 299 [M+H] + . Anal. Calcd for C 18 H 18 O 4 : C, 72.47; H, 6.08. Found: C, 72.69; H, 6.31.
Compound 3c: 76%; colorless oil, IR (film) 1720, 1318, 1228 cm −1 ; 1 H NMR (CDCl 3 , 300 MHz) δ 1.25 (t, J = 7.2 Hz, 3H), 1.34 (t, J = 7.2 Hz, 3H), 2.41 (s, 3H), 4.24 (q, J = 7.2 Hz, 2H), 4.32 (q, J = 7.2 Hz, 2H), 4.42 (s, 2H) 6.77 (d, J = 6.6 Hz, 1H), 7.25 (t, J = 7.8 Hz, 1H), 7.38-7.50 (m, 2H), 7.67 (d, J = 8.4 Hz, 1H), 7.76-7.86 (m, 1H), 7.79 (d, J = 1.8 Hz, 1H), 7.90-7.96 (m, 1H), 8.29 (d, J = 1.8 Hz, 1H); 13 C NMR (CDCl 3 , 75 MHz) δ 14.21, 14.28, 16.89, 36.42, 61.04, 61.27, 123.23, 125.53, 125.72, 125.79, 126.19, 127.19, 128.00, 128.82, 129.43, 131.81, 132.32, 133.72, 133.97, 134.96, 140.11, 143.02, 165.92, 167.96; ESIMS m/z 377 [M+H] + . Anal. Calcd for C 24 H 24 O 4 : C, 76.57; H, 6.43. Found: C, 76.45; H, 6.68.
Compound 3d: 71%; colorless oil, IR (film) 1720, 1368, 1228 cm −1 ; 1 H NMR (CDCl 3 , 300 MHz) δ 1.39 (t, J = 7.2 Hz, 3H), 1.41 (t, J = 7.2 Hz, 3H), 2.48 (s, 3H), 4.26 (s, 2H), 4.37 (q, J = 7.2 Hz, 2H), 4.38 (q, J = 7.2 Hz, 2H), 7.26 (dd, J = 8.4 and 1.8 Hz, 1H), 7.38-7.47 (m, 3H), 7.68-7.73 (m, 1H), 7.76 (d, J = 8.4 Hz, 1H), 7.76-7.81 (m, 1H), 8.04 (d, J = 1.8 Hz, 1H), 8.36 (d, J = 1.8 Hz, 1H); 13 C NMR (CDCl 3 , 75 MHz) δ 14.26, 14.30, 17.04, 40.01, 61.13, 61.23, 125.48, 126.07, 126.63, 126.95, 127.52, 127.57, 127.91, 128.19, 129.48, 132.09, 132.53, 133.49, 134.08, 136.80, 140.41, 143.02, 165.99, 167.91; ESIMS m/z 377 [M+H] + .
Compound 3e: 66%; colorless oil, IR (film) 1720, 1316, 1228 cm −1 ; 1 H NMR (CDCl 3 , 300 MHz) δ 1.33 (t, J = 7.2 Hz, 3H), 1.34 (t, J = 7.2 Hz, 3H), 2.49 (s, 3H), 3.50-3.63 (m, 2H), 4.31 (q, J = 7.2 Hz, 2H), 4.32 (q, J = 7.2 Hz, 2H), 6.21 (dd, J = 15.9 and 4.2 Hz, 1H), 6.28 (dd, J = 15.9 and 2.4 Hz, 1H), 7.09-7.27 (m, 5H), 7.92 (d, J = 1.8 Hz, 1H), 8.24 (d, J = 1.8 Hz, 1H); 13 C NMR (CDCl 3 , 75 MHz) δ 14.28, 14.32, 16.75, 37.20, 61.12, 61.23, 126.10, 127.27, 127.32, 127.91, 128.49, 129.27, 131.53, 132.30, 133.26, 137.11, 140.09, 142.54, 166.01, 167.95; ESIMS m/z 353 [M+H] + . Anal. Calcd for C 22 H 24 O 4 : C, 74.98; H, 6.86. Found: C, 75.12; H, 6.93.
Compound 3f: 69%; colorless oil, IR (film) 1721, 1303, 1229, 1177 cm −1 ; 1 H NMR (CDCl 3 , 300 MHz) δ 1.39 (t, J = 7.2 Hz, 3H), 1.41 (t, J = 7.2 Hz, 3H), 2.53 (s, 3H), 4.06 (s, 2H), 4.37 (q, J = 7.2 Hz, 2H), 4.38 (q, J = 7.2 Hz, 2H), 5.89 (dd, J = 3.3 and 0.9 Hz, 1H), 6.27 (dd, J = 3.3 and 1.8 Hz, 1H), 7.32 (dd, J = 1.8 and 0.9 Hz, 1H), 7.97 (d, J = 1.8 Hz, 1H), 8.33 (d, J = 1.8 Hz, 1H); 13 C NMR (CDCl 3 , 75 MHz) δ 14.25, 14.27, 16.69, 32.70, 61.11, 61.23, 106.56, 110.30, 127.91, 129.64, 132.34, 133.58, 138.16, 141.58, 142.68, 152.90, 165.84, 167.79; ESIMS m/z 317 [M+H] + .
Compound 3g: 53%; colorless oil, IR (film) 2957, 2930, 1722, 1315, 1226 cm −1 ; 1 H NMR (CDCl 3 , 300 MHz) δ 0.90 (t, J = 7.2 Hz, 3H), 1.25-1.38 (m, 6H), 1.40 (t, J = 7.2 Hz, 3H), 1.41 (t, J = 7.2 Hz, 3H), 1.54-1.65 (m, 2H), 2.53 (s, 3H), 2.69 (t, J = 7.8 Hz, 2H), 4.38 (q, J = 7.2 Hz, 2x2H), 7.92 (d, J = 1.8 Hz, 1H), 8.24 (d, J = 1.8 Hz, 1H); 13 C NMR (CDCl 3 , 75 MHz) δ 14.04, 14.27, 14.32, 16.50, 22.57, 29.25, 30.20, 31.63, 33.79, 61.02, 61.13, 127.56, 128.55, 132.08, 132.73, 141.85, 142.90, 166.18, 168.15; ESIMS m/z 321 [M+H] + . Anal. Calcd for C 19 H 28 O 4 : C, 71.22; H, 8.81. Found: C, 71.47; H, 8.79.
Compound 3h: 69%; colorless oil, IR (film) 1721, 1317, 1228 cm −1 ; 1 H NMR (CDCl 3 , 300 MHz) δ 1.04 (t, J = 7.5 Hz, 3H), 1.31 (t, J = 7.2 Hz, 3H), 1.33 (t, J = 7.2 Hz, 3H), 2.86 (q, J = 7.5 Hz, 2H), 4.06 (s, 2H), 4.29 (q, J = 7.2 Hz, 2H), 4.31 (q, J = 7.2 Hz, 2H), 6.97-7.04 (m, 2H), 7.08-7.23 (m, 3H), 7.88 (d, J = 1.8 Hz, 1H), 8.23 (d, J = 1.8 Hz, 1H); 13 C NMR (CDCl 3 , 75 MHz) δ 14.24, 14.30, 15.01, 23.37, 38.77, 61.09, 61.24, 126.28, 127.98, 128.47, 128.52, 129.67, 132.10, 134.57, 139.90, 139.91, 148.50, 165.95, 167.91; ESIMS m/z 341 [M+H] + .
Compound 3i: 48%; pale yellow oil, IR (film) 1722, 1368, 1245 cm −1 ; 1 H NMR (CDCl 3 , 300 MHz) δ 0.92, (t, J = 7.2 Hz, 3H), 1.41 (t, J = 7.2 Hz, 3H), 3.82 (s, 2H), 3.99 (q, J = 7.2 Hz, 2H), 4.40 (q, J = 7.2 Hz, 2H), 6.75 (d, J = 8.4 Hz, 2H), 7.00-7.07 (m, 2H), 7.13 (d, J = 8.4 Hz, 2H), 7.29-7.36 (m, 3H), 8.04 (d, J = 1.8 Hz, 1H), 8.35 (d, J = 1.8 Hz, 1H); 13 C NMR (CDCl 3 , 75 MHz) δ 13.59, 14.31, 38.60, 61.08, 61.35, 127.48, 127.91, 128.34, 128.57, 128.65, 129.75, 129.95, 131.86, 133.32, 133.60, 138.54, 138.63, 140.04, 145.83, 165.66, 167.74; ESIMS m/z 423 [M+H] + , 425 [M+H+2] + . Anal. Calcd for C 25 H 23 ClO 4 : C, 71.00; H, 5.48. Found: C, 71.13; H, 5.71.
Compound 4a: 42%; colorless oil, IR (film) 1721, 1310, 1233, 1176 cm −1 ; 1 H NMR (CDCl 3 , 300 MHz) δ 0.92 (t, J = 7.2 Hz, 3H), 1.41 (t, J = 7.2 Hz, 3H), 2.04 (s, 3H), 2.54 (s, 3H), 3.96 (q, J = 7.2 Hz, 2H), 4.39 (q, J = 7.2 Hz, 2H), 7.09- 7.15 (m, 2H), 7.31-7.43 (m, 3H), 8.09 (s, 1H); 13 C NMR (CDCl 3 , 75 MHz) δ 13.59, 14.29, 17.64, 17.67, 60.75, 61.15, 127.01, 127.89, 128.15, 128.59, 129.54, 130.63, 137.38, 140.56, 141.13, 144.33, 167.96, 168.02; ESIMS m/z 327 [M+H] + . Anal. Calcd for C 20 H 22 O 4 : C, 73.60; H, 6.79. Found: C, 73.75; H, 6.92.
Acknowledgements
Acknowledgments.This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2012R1A1B3000541). Spectroscopic data were obtained from the Korea Basic Science Institute, Gwangju branch.
References
Lee M. J. , Park D. Y. , Lee K. Y. , Kim J. N. 2006 Tetrahedron Lett. 47 1833 - 1837    DOI : 10.1016/j.tetlet.2005.12.134
Kvita V. 1990 Helv. Chim. Acta 73 411 - 416    DOI : 10.1002/hlca.19900730220