Ketene recognizes 1,3-dienes in their s-Cis forms through [4 ± 2] (Diels-Alder) and [2 ± 2] (Staudinger) reactions. An innovation of ketene chemistry

Journal of the American Chemical Society

Volumn 121, Issue 20, 1999, Pages 4771-4786

  Machiguchi, Takahisa ^a   Hasegawa, Toshio ^a   Ishiwata, Akihiro ^b   Terashima, Shiro ^b   Yamabe, Shinichi ^c   Minato, Tsutomu ^d  

^a SAITAMA UNIVERSITY   (Japan)

^b SAGAMI CHEMICAL RESEARCH CENTER   (Japan)

^c NARA UNIVERSITY OF EDUCATION   (Japan)

^d NARA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE; KETENE DERIVATIVE;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; MOLECULAR INTERACTION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY;

EID: 0033606252     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja990072u     Document Type: Article

References (111)

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47. a] cycloadditions. The next lowest unoccupied molecular orbital, (lu + 1)mo, of ketenes could overlap efficiently with the highest occupied molecular orbital (HOMO) of olefins orthogonally in Scheme 2.
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57. a] pathway in Scheme 2.
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61. In Scheme 3a, the reaction of diphenylketene (1) with 2-methoxybutadiene leads to the isolation of an isomer of the real intermediate. The product is thought to be formed via a [4 + 2] cycloadduct and its isomerization, hydrogen 1,3-shift.
62. Similarly, a 1,4-cycloadduct between bis(trifluoromethyl)ketene and 1,3-butadiene isomerizes easily to give a pyran (Scheme 3b). England, D. C.; Krespan, C. G. J. Am. Chem. Soc. 1965, 87, 4019-4020. England, D. C.; Krespan, C. G. J. Am. Chem. Soc. 1966, 88, 5582-5587.
63. Similarly, a 1,4-cycloadduct between bis(trifluoromethyl)ketene and 1,3-butadiene isomerizes easily to give a pyran (Scheme 3b). England, D. C.; Krespan, C. G. J. Am. Chem. Soc. 1965, 87, 4019-4020. England, D. C.; Krespan, C. G. J. Am. Chem. Soc. 1966, 88, 5582-5587.
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79. 11d,15,14b etc.) afford cyclobutanones.
80. C = 150 and 70-90 ppm, indicating an enol carbon and methine (or methylene) ones, respectively.
81. 1H NMR monitoring.
82. 1H long-range selective decoupling (LSPD).
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86. 1H) spectral data show that the [4 + 2] cycloadduct 10 is formed by attack of diphenylketene to the terminal 1 and 4 positions of the diene 2.
87. 1H relationship demonstrates that the structure of 10 has a norbornene moiety.
88. 1H signals shift to downfield prominently.
89. Roberts and co-workers recently reported that the reaction gave an equilibrium mixture of 7 and 11. See ref 39.
90. 3. The measurements were performed at -60 °C. This conversion proceeds without any sign of melting as a crystal-to-crystal phase reaction. Cf.: Machiguchi, T.; Hasegawa, T.; Ito, S.; Mizuno, H. J. Am. Chem. Soc. 1989, 111, 1920-1921.
91. Wang, X.; Houk, K. N. J. Am. Chem. Soc. 1990, 112, 1754-1756.
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97. 39
98. 9b,15b,41)] in low yield (21%) accompanied by the dihydropyran 12 (12%) and most of the unreacted ketene 1. When reaction 3 was carried out under mild conditions [room temperature, 3 months, no solvent (see the Supporting Information); 40 °C, 40 days, no solvent (iii in Scheme 5)], the product obtained exclusively has been identified to be α-methylenedihydropyran 12. Cyclobutanone 8 was isolated as the intermediate of the reaction (xiii in Scheme 6).
99. 13C) and MS data are in the Supporting Information.
100. Recrystallization from cold pentane-ether gave pure crystals with the melting point. The crystals thus obtained remained unchanged at least over half a year at -80 °C. On standing at 0 °C below the melting temperature, however, the crystals of 10 were converted spontaneously to a solid yielding exclusively a [2 + 2]-type cycloadduct 6 (vii in Scheme 6).
101. 13C NMR measurement.
102. -1.
103. -1.
104. 13C) and MS data are in the Supporting Information.
105. 18O: C, 87.56; H, 6.61. Found: C, 87.47; H, 6.62.
106. 20O: C, 86.92; H, 7.29. Found: C, 86.75; H, 7.29.
107. Compound 14 is also obtained from the reaction of 1 with 4 under photoirradiation (Otto, P. Ph.D. Dissertation, University of Munich, 1970). We thank Prof. Rolf Huisgen for his kind information.
108. 9b,15b,41 The reason is not clear. Regarding this discrepancy, we have repeatedly examined reaction 3 with special care in two research groups (Saitama University and Sagami Chemical Research Center) independently. The IR spectrum and the melting point data of cyclobutanone 8 (mp 82-83 °C, measured on a Yanako MP-3 micro-melting point apparatus) obtained at the latter group were identical with those at the former group. By our hands, crystals of cyclobutanone 8 were found to show neither polymorphism nor formation of any hydrates.
109. The measurements were performed using a 2.0-mm (i.d.) capillary (Japan Precision Instrument, N-502A), which was loaded inside of a 5Φ-NMR tube (N-5P), to keep a concentration similar to that under preparative conditions.
110. Onsager, L. J. Am. Chem. Soc. 1936, 58, 1486-1493.
111. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. GAUSSIAN 94, Revision C.4; Gaussian, Inc.: Pittsburgh, PA, 1995.