The Diverted Di-π-Methane Rearrangement; Mechanistic and Exploratory Organic Photochemistry

Organic Letters

Volumn 4, Issue 7, 2002, Pages 1155-1158

  Zimmerman, Howard E ^a   Chen, Wensheng ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

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EID: 0001152057     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol025564h     Document Type: Article

References (8)

1. This is paper 265 of our general series. For paper 262 see: Zimmerman, H. E.; Wang, P. Helv. Chim. Acta 2001, 65, 1342-1346.
2. Zimmerman, H. E.; Armesto, D. Chem. Rev. 1996, 96, 3065-3112.
3. (a) Zimmerman, H. E.; Armesto, D.; Amezua, M. G.; Gannett, T. P.; Johnson, R. P. J. Am. Chem. Soc. 1979, 101, 6367-6383.
4. (b) Zimmerman, H. E.; Factor, R. E. Tetrahedron 1981, 37, Supplement 1, 125-141.
5. (c) Zimmerman, H. E.; Cirkva, V. J. Org. Chem. 2001, 66, 1839-1856.
6. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A.6; Gaussian, Inc.: Pittsburgh, PA, 1998.
7. Typical Procedure. Preparative Sensitized Irradiation of 1,1-Dimethoxycarbonyl-3,3-dimethyl-5,5-diphenylpentadiene 6. A solution of 200 mg (0.55 mmol) of 1,1-dimethoxycarbonyl-3,3-dimethyl-5,5-diphenyl-1,4-pentadiene and 8.5 g of acetophenone (70.8 mmol) in 210 mL of benzene was irradiated for 40 min through a 0.20 M cupric sulfate filter, which cuts off below 300 nm. Concentration in vacuo gave a yellow oil that was subjected to bulb-to-bulb distillation (0.05 Torr, 40°C) to remove acetophenone. The remaining yellow oil was chromatographed on a 4 cm × 70 cm column eluted with 5% ether/hexane. Fraction 1 gave 0.717 g of acetophenone. Fraction 2 gave 10 mg of overlap material. Fraction 3 gave 52 mg of 1,1-dimethyl-2,2-diphenyl-3-(2,2-dimethoxycarbonylvinyl)-cyclopropane 7, mp 143-144°C. Fraction 4 gave 110 mg of trans-2-methoxycarbonyl-3-(2,2-diphenylvinyl)-4,4-dimethyltetrahydrofuran-2-one 8, mp 108-109 °C
8. The structures of compounds 2, 7-9, and 24 were determined by single-crystal X-ray diffractometry and the remainder by NMR analysis; see Supporting Information for tables and data.