Abstract
The photo-dehydro-Diels-Alder reaction (PDDA), a new photochemical route to naphthalenes is presented. The [4+2] cycloaddition takes place between 3-arylynones and arylacetylenes, in which these moieties may be located in two molecules (intermolecular PDDA, 1 ) or in the same molecule (intramolecular PDDA, 5 and 9 ). Especially the latter approach is attractive from a preparative point of view and permits a straightforward access to highly functionalized naphthalenes. The irradiation of unsymmetrical reactants 9 provides, in contrast to symmetrical reactants 5 , two isomeric naphthalenes. We found that the regioselectivity can be easily influenced by suitably located substituents in the aromatic rings and by blocking undesired positions. Notably, the PDDA may be used for the preparation of binaphthyls, as shown by the formation of 14 and 16 . The mechanism of the PDDA was elucidated by spectroscopic analyses and theoretical (DFT) calculations.
Key words
dehydro Diels-Alder reaction - naphthalenes - binaphthyls - photocyclization
References
1a Norrish RGW.
Appleyard MES.
J. Chem. Soc.
1934,
874
1b Yang NC.
Yang D.-DH.
J. Am. Chem. Soc.
1958,
80:
2913
1c Wagner PJ. In CRC Handbook of Organic Photochemistry and Photobiology
2nd ed.:
Horspool WM.
Lenci F.
CRC Press;
Boca Raton:
2003.
p.52
1d Wagner PJ. In CRC Handbook of Organic Photochemistry and Photobiology
2nd ed.:
Horspool WM.
Lenci F.
CRC Press;
Boca Raton:
2003.
p.58
1e Wessig P. In Radicals in Organic Synthesis
Renaud P.
Sibi MP.
VCH-Wiley;
Weinheim:
2001.
1f Wessig P. In CRC Handbook of Organic Photochemistry and Photobiology
2nd ed.:
Horspool WM.
Lenci F.
CRC Press;
Boca Raton:
2003.
p.57
2a Jones G.
Org. Photochem.
1981,
5:
1
2b Griesbeck AG. In CRC Handbook of Organic Photochemistry and Photobiology
2nd ed.:
Horspool WM.
Lenci F.
CRC Press;
Boca Raton:
2003.
p.59
2c Griesbeck AG. In CRC Handbook of Organic Photochemistry and Photobiology
2nd ed.:
Horspool WM.
Lenci F.
CRC Press;
Boca Raton:
2003.
p.60
3 Wessig P.
Mühling O. In Synthetic Organic Photochemistry
Griesbeck AG.
Mattay J.
Marcel Decker;
New York:
2005.
p.41-88
4 The introduction of electron-donating groups, which facilitate oxidative degradation of aromatic rings, reduce the Norrish-Yang reactivity of corresponding ketones dramatically.1c,d
5 Michael A.
Bucher JE.
Ber. Dtsch. Chem. Ges.
1895,
28:
2511
6 Pfeiffer P.
Möller W.
Ber. Dtsch. Chem. Ges.
1907,
40:
3841
7a Bucher JE.
J. Am. Chem. Soc.
1910,
32:
212
7b Haworth RD.
Sheldrick G.
J. Chem. Soc.
1935,
636
7c Haworth RD.
Kelly W.
J. Chem. Soc.
1936,
745
7d Baddar FG.
El-Assal LS.
Doss NA.
J. Chem. Soc.
1959,
1027
7e Brown D.
Stevenson R.
J. Org. Chem.
1965,
30:
1759
7f Klemm LH.
Gopinath KW.
Lee DH.
Kelley FW.
Trod E.
McGuire TM.
Tetrahedron
1966,
22:
1797
8 Whitlock HW.
Wu E.-M.
Whitlock BJ.
J. Org. Chem.
1969,
34:
1857
9 Müller E.
Sauerbier M.
Streichfuß D.
Thomas R.
Winter W.
Zountsas G.
Liebigs Ann. Chem.
1971,
750:
63
10 Müller E.
Odenigbo G.
Liebigs Ann. Chem.
1975,
1435
11 Wagner F.
Meier H.
Tetrahedron
1974,
30:
773
12a Chabala JC.
Vincent JE.
Tetrahedron Lett.
1978,
19:
937
12b Yamaguchi M.
Shibato K.
Fujiwara S.
Hirao I.
Synthesis
1986,
421
12c Doubsky J.
Streinz L.
Leseticky L.
Koutek B.
Synlett
2003,
937
13 Yashina OG.
Sarwaa TW.
Kaigorodowa TD.
Wereschtschagin LI.
J. Org. Chem. USSR (Engl. Transl.)
1968,
4:
2032 ; Zh. Org. Khim. ; 1968 , 4 : 2104
14a Dess DB.
Martin JC.
J. Org. Chem.
1983,
48:
4156
14b Dess DB.
Martin JC.
J. Am. Chem. Soc.
1991,
113:
7277
15a Miyashita A.
Yasuda A.
Takaya H.
Toriumi K.
Ito T.
Souchi T.
Notori R.
J. Am. Chem. Soc.
1980,
102:
7932
15b Takaya H.
Mashima K.
Koyano K.
Yagi M.
Kumobayashi H.
Taketomi T.
Akutagawa S.
Notori R.
J. Org. Chem.
1986,
51:
629
16 We thank Dr. B. Ziemer for performing the X-ray structure analysis of 16 . Details of the structure investigation are available on request from the Cambridge Crystallographic Data Centre, on quoting the depository number CCDC 266349.
17 El-Sayed MA.
J. Chem. Phys.
1963,
38:
2834
18 Woodward RB.
Hoffmann R.
J. Am. Chem. Soc.
1965,
87:
395
19a Becke AD.
J. Chem. Phys.
1993,
98:
5648
19b Lee C.
Yang W.
Parr RG.
Phys. Rev. B
1988,
37:
785
19c Miehlich B.
Savin A.
Stoll H.
Preuss H.
Chem. Phys. Lett.
1989,
157:
200
19d Parr RG.
Yang W.
Density-Functional Theory of Atom and Molecules
Oxford University Press;
New York:
1989.
20a Ditchfield R.
Hehre WJ.
Pople JA.
J. Chem. Phys.
1971,
54:
724
20b Hariharan PC.
Pople JA.
Chem. Phys. Lett.
1972,
66:
217
20c Rassolov VA.
Ratner MA.
Pople JA.
Redfern PC.
Curtiss LA.
J. Comp. Chem.
2001,
22:
976
20d McLean AD.
Chandler GS.
J. Chem. Phys.
1980,
72:
5639
20e Krishnan R.
Binkley JS.
Seeger R.
Pople JA.
J. Chem. Phys.
1980,
72:
650
21 Frisch MJ.
Trucks GW.
Schlegel HB.
Scuseria GE.
Robb MA.
Cheeseman JR.
Montgomery JA.
Vreven T.
Kudin KN.
Burant JC.
Millam JM.
Iyengar SS.
Tomasi J.
Barone V.
Mennucci B.
Cossi M.
Scalmani G.
Rega N.
Petersson GA.
Nakatsuji H.
Hada M.
Ehara M.
Toyota K.
Fukuda R.
Hasegawa J.
Ishida M.
Nakajima T.
Honda Y.
Kitao O.
Nakai H.
Klene M.
Li X.
Knox JE.
Hratchian HP.
Cross JB.
Adamo C.
Jaramillo J.
Gomperts R.
Stratmann RE.
Yazyev O.
Austin AJ.
Cammi R.
Pomelli C.
Ochterski JW.
Ayala PY.
Morokuma K.
Voth GA.
Salvador P.
Dannenberg JJ.
Zakrzewski VG.
Dapprich S.
Daniels AD.
Strain MC.
Farkas O.
Malick KD.
Rabuck AD.
Raghavachari K.
Foresman JB.
Ortiz JV.
Cui Q.
Baboul AG.
Clifford S.
Cioslowski J.
Stefanov BB.
Liu G.
Liashenko A.
Piskorz P.
Komaromi I.
Martin RL.
Fox DJ.
Keith T.
Al-Laham MA.
Peng CY.
Nanayakkara A.
Challacombe M.
Gill PMW.
Johnson B.
Chen W.
Wong MW.
Gonzalez C.
Pople JA.
Gaussian 03, Revision B.04
Gaussian, Inc.;
Pittsburgh PA:
2003.
22a Scaiano JC.
Tetrahedron
1982,
38:
819
22b Salem L.
Rowland C.
Angew. Chem., Int. Ed. Engl.
1972,
11:
92
22c Griesbeck AG.
Mauder H.
Stadtmüller S.
Acc. Chem. Res.
1994,
27:
70
23 Yamaguchi K.
Jensen F.
Dorigo A.
Houk KN.
Chem. Phys. Lett.
1988,
149:
537
24 Cioslowski J.
J. Am. Chem. Soc.
1989,
111:
8333
