Abstract
Oximes of 5,5-disubstituted 1-azapenta-1,4-dien-3-ones 3 underwent 1,5-cyclization reactions yielding
indenole derivatives 4 in moderate to good
yields upon treatment with an excess of trifluoromethanesulfonic
acid. Similarly, the hydrazone 3g led to
indenole 4f upon protonation. The reaction
could also be successfully applied to the synthesis of benzo[b]cyclopenta[d]thiophene 5 starting
from 3f. Products of a competing aza-Nazarov
reaction were not observed. The reaction mechanism is explained
by assuming the involvement of dicationic intermediates, generated
by superelectrophilic solvation, similar to that of known Nazarov
and aza-Nazarov-type transformations. Quantum chemical calculations
of reaction energies and activation barriers are discussed with
respect to the experimental results.
Key words
cyclization - carbocations - penta-1,4-dien-3-ones - indenoles - quantum chemical
calculations
References
<A NAME="RT08108SS-1A">1a</A>
Klumpp DA.
Zhang Y.
O’Connor MJ.
Estevens PM.
Almeida LS.
Org.
Lett.
2007,
9:
3085
<A NAME="RT08108SS-1B">1b</A>
Suzuki T.
Ohwada T.
Shudo K.
J.
Am. Chem. Soc.
1997,
119:
6774
<A NAME="RT08108SS-2A">2a</A>
Ciufolini MA.
Roschangar F.
Tetrahedron
1997,
53:
11049
<A NAME="RT08108SS-2B">2b</A>
Matoba K.
Itoh K.
Yamazaki T.
Nagata M.
Chem. Pharm. Bull.
1981,
29:
2442
<A NAME="RT08108SS-2C">2c</A>
Matoba K.
Miyata Y.
Yamazaki T.
Chem.
Pharm. Bull.
1983,
31:
476
<A NAME="RT08108SS-2D">2d</A>
Matoba K.
Terada T.
Sugiuara M.
Yamazaki T.
Heterocycles
1987,
26:
55
<A NAME="RT08108SS-2E">2e</A>
Aftfah A.
Abu-Shuheil MY.
Hill J.
Tetrahedron
1990,
46:
6483
<A NAME="RT08108SS-3A">3a</A>
Olah GA.
Klumpp DA.
Superelectrophiles and Their Chemistry
Wiley;
New
York:
2007.
<A NAME="RT08108SS-3B">3b</A>
Olah GA.
Angew. Chem., Int. Ed. Engl.
1993,
32:
767
<A NAME="RT08108SS-3C">3c</A>
Olah GA.
Klumpp DA.
Acc.
Chem. Res.
2004,
37:
211
<A NAME="RT08108SS-3D">3d</A>
Lammertsma K.
Schleyer P. v. R.
Schwarz H.
Angew. Chem.,
Int. Ed. Engl.
1989,
28:
1321
<A NAME="RT08108SS-4A">4a</A> inventors; Kurakay
Co. Ltd., Jpn. Kokai Tokkya Koho JP 81113740.
; Chem. Abstr. 1982, 96, 68724b
<A NAME="RT08108SS-4B">4b</A> inventors; Kurakay Co.
Ltd., Jpn. Kokai Tokkya Koho JP 8204945.
; Chem. Abstr. 1982, 96, 19935u
<A NAME="RT08108SS-4C">4c</A>
Samula K.
Cichy B.
Acta Pol. Pharm.
1985,
42:
256 ; Chem. Abstr.
1986, 105, 17193
<A NAME="RT08108SS-4D">4d</A>
Anstead GM.
Altenbach RJ.
Wilson SR.
Katzenellenbogen JA.
J.
Med. Chem.
1988,
31:
1316
<A NAME="RT08108SS-4E">4e</A>
Anstead GM.
Katzenellenbogen JA.
J. Med.
Chem.
1988,
31:
1754
<A NAME="RT08108SS-4F">4f</A>
Anstead GM.
Wilson SR.
Katzenellenbogen JA.
J. Med. Chem.
1989,
32:
2163
<A NAME="RT08108SS-4G">4g</A>
Watanabe N.
Ikeno A.
Minato H.
Nakagawa H.
Kohayakawa C.
Tsuji J.
J. Med. Chem.
2003,
46:
3961
<A NAME="RT08108SS-4H">4h</A>
Hagishita S.
Yamada M.
Shirahase K.
Okada T.
Murakami Y.
Ito Y.
Matsuura T.
Wada M.
Kato T.
Ueno M.
Chikazawa Y.
Yamada K.
Ono T.
Teshirogi I.
Ohtani M.
J. Med. Chem.
1996,
39:
3636
<A NAME="RT08108SS-4I">4i</A>
Yang L.
Guo L.
Pasternak A.
Mosley R.
Rohrer S.
Birzin E.
Foor F.
Cheng K.
Schaeffer J.
Patchett AA.
J. Med. Chem.
1998,
41:
2175
<A NAME="RT08108SS-4J">4j</A>
Reggio PH.
Basu-Dutt S.
Barnett-Norris J.
Castro MT.
Hurst DP.
Seltzman HH.
Roche MJ.
Gilliam AF.
Thomas BF.
Stevenson LA.
Pertwee RG.
Abood ME.
J. Med. Chem.
1998,
41:
5177
<A NAME="RT08108SS-4K">4k</A>
Clive DLJ.
Yu M.
Chem.
Commun.
2002,
2380
<A NAME="RT08108SS-4L">4l</A>
Jobashi T.
Kawai A.
Kawai S.
Maeyama K.
Oike H.
Yoshida Y.
Yonezawa N.
Tetrahedron
2006,
62:
5717
<A NAME="RT08108SS-4M">4m</A>
Reddy PB.
Singh PP.
Sawant SD.
Koul S.
Taneja SC.
Kumar HMS.
ARKIVOC
2006,
(xiii):
142
<A NAME="RT08108SS-5A">5a</A>
Quan LG.
Gevorgyan V.
Yamamato Y.
J. Am. Chem. Soc.
1999,
121:
3545
<A NAME="RT08108SS-5B">5b</A>
Quan LG.
Gevorgyan V.
Yamamato Y.
J. Am. Chem. Soc.
1999,
121:
9485
<A NAME="RT08108SS-5C">5c</A>
Gevorgyan V.
Quan LG.
Yamamato Y.
Tetrahedron Lett.
1999,
40:
4089
<A NAME="RT08108SS-5D">5d</A>
Liebeskind LS.
Gasdaska JR.
McCallum JS.
Tremont SJ.
J.
Org. Chem.
1989,
54:
669
<A NAME="RT08108SS-5E">5e</A>
Vicente J.
Abad J.-A.
Lopez-Pelaez B.
Martinez-Viviente E.
Organometallics
2002,
21:
58
<A NAME="RT08108SS-5F">5f</A>
Rayabarapu DK.
Yang C.-H.
Cheng C.-H.
J. Org. Chem.
2003,
68:
6726
<A NAME="RT08108SS-5G">5g</A>
Shintani R.
Okamura K.
Hayashi T.
Chem.
Lett.
2005,
34:
1294
<A NAME="RT08108SS-5H">5h</A>
Matsuda T.
Makino M.
Murakami M.
Chem.
Lett.
2005,
34:
1416
<A NAME="RT08108SS-5I">5i</A>
Tsukamoto H.
Ueno T.
Kondo Y.
Org.
Lett.
2007,
9:
3033
<A NAME="RT08108SS-6A">6a</A>
Barré R.
Kohler EP.
J.
Am. Chem. Soc.
1928,
50:
2036
<A NAME="RT08108SS-6B">6b</A>
Kohler EP.
Weiner N.
J. Am. Chem.
Soc.
1934,
56:
434
<A NAME="RT08108SS-6C">6c</A>
Wall DK.
McMaster MC.
Cromwell NH.
J. Org. Chem.
1969,
4:
1124
<A NAME="RT08108SS-7">7</A>
Faza ON.
Lopez CS.
Alvarez R.
de Lera AR.
Chem. Eur. J.
2004,
10:
4324
<A NAME="RT08108SS-8">8</A> For NICS values, see:
Schleyer P. v. R.
Maerker C.
Dransfeld A.
Jiao H.
van Eikema Hommes NJR.
J. Am. Chem. Soc.
1996,
118:
6317
<A NAME="RT08108SS-9A">9a</A>
Chandrasekhar J.
Jemmis ED.
Schleyer P.v.R..
Tetrahedron Lett.
1979,
20:
3707
<A NAME="RT08108SS-9B">9b</A>
Dewar MJS.
J. Am. Chem. Soc.
1984,
106:
669
<A NAME="RT08108SS-10A">10a</A>
Heilbronner E.
Tetrahedron Lett.
1964,
1923
<A NAME="RT08108SS-10B">10b</A>
Zimmermann HE.
J. Am. Chem. Soc.
1966,
88:
1564
<A NAME="RT08108SS-10C">10c</A>
Zimmerman HE.
Acc. Chem. Res.
1971,
4:
272
<A NAME="RT08108SS-11A">11a</A>
Dieker J.
Fröhlich R.
Würthwein E.-U.
Eur. J. Org. Chem.
2006,
5339
<A NAME="RT08108SS-11B">11b</A>
Ghavtadze N.
Ph.D. Thesis, in preparation
University
Münster;
Germany:
2008. and unpublished
results
<A NAME="RT08108SS-11C">11c</A>
Ghavtadze N.
Fröhlich R.
Würthwein E.-U.
Eur. J. Org. Chem.
2008,
3656
<A NAME="RT08108SS-12">12</A>
Data sets were collected with a Nonius
KappaCCD diffractometer, equipped with a rotating anode generator. Programs
used: data collection COLLECT;¹³ data
reduction Denzo-SMN,¹4 absorption correction
SORTAV,¹5 Denzo,¹6 structure
solution SHELXS-97,¹7 structure refinement SHELXL-97,¹8 and
graphics SCHAKAL.¹9 CCDC numbers 688078-688079
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html
[or
from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK, fax: +44(1223) 336 033, E-mail: deposit@ccdc.cam.ac.uk].
<A NAME="RT08108SS-13">13</A>
COLLECT
Nonius
B. V.;
Delft:
1998.
<A NAME="RT08108SS-14">14</A>
Otwinowski Z.
Minor W. In Methods
in Enzymology
Vol. 276:
Carter CW.
Sweet RM.
Academic
Press;
New York:
1997.
p.307
<A NAME="RT08108SS-15A">15a</A>
Blessing RH.
Acta Crystallogr.,
Sect. A
1995,
51:
33
<A NAME="RT08108SS-15B">15b</A>
Blessing RH.
J. Appl. Crystallogr.
1997,
30:
421
<A NAME="RT08108SS-16">16</A>
Otwinowski Z.
Borek D.
Majewski W.
Minor W.
Acta Crystallogr., Sect. A
2003,
59:
228
<A NAME="RT08108SS-17">17</A>
Sheldrick GM.
Acta
Crystallogr., Sect. A
1990,
46:
467
<A NAME="RT08108SS-18">18</A>
Sheldrick GM.
Acta
Crystallogr., Sect. A
2008,
64:
112
<A NAME="RT08108SS-19">19</A>
Keller E.
Schakal
97, University of Freiburg,
1997,
<A NAME="RT08108SS-20A">20a</A>
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.
Bakken V.
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 DK.
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 C.02
Gaussian, Inc.;
Wallingford
CT:
2004.
<A NAME="RT08108SS-20B">20b</A>
Details of the quantum
chemical calculations (Gaussian archive entries) may be obtained
from E.-U.W. upon request.
<A NAME="RT08108SS-21">21</A>
Grimme S.
J.
Chem. Phys.
2003,
118:
9095
<A NAME="RT08108SS-22">22</A>
Ashton WT.
Doss GA.
J. Heterocycl. Chem.
1993,
30:
307
<A NAME="RT08108SS-23">23</A>
Neidlein R.
Feistauer H.
Helv. Chim. Acta
1996,
79:
895
