RSS-Feed abonnieren
DOI: 10.1055/s-0030-1260533
Stereoselective Synthesis of Pyrrolo[1,2-a]indoles from Allenes in PEG-400 as the Reaction Medium
Publikationsverlauf
Publikationsdatum:
20. April 2011 (online)
![](https://www.thieme-connect.de/media/synlett/201109/lookinside/thumbnails/10.1055-s-0030-1260533-1.jpg)
Abstract
Base-catalyzed domino cyclization of allenes with 3-chloro-2-formylindoles in PEG-400 was investigated. Pyrroloindoles were formed stereoselectively as single products. The structure of the product depends on the type of allene used. Two compounds have been characterized by single crystal X-ray diffraction.
Key words
allenes - 3-chloro-2-formylindole - domino cyclization - pyrroloindoles - PEG-400
- Supporting Information for this article is available online:
- Supporting Information
-
1a
Orlemans EOM.Verboom W.Scheltinga MW.Reinhoudt DN.Lelieveld P.Fiebig HH.Winterhalter BR.Double JA.Bibby MC. J. Med. Chem. 1989, 32: 1612 -
1b
Galm U.Hanger MH.Lanen SGV.Ju J.Thorson JS.Shen B. Chem. Rev. 2005, 105: 739 -
1c
Paris D.Cottin M.Demonchaux P.Augert G.Dupassieux P.Lenoir P.Peck MJ.Jasserand D. J. Med. Chem. 1995, 38: 669 -
1d
Wilson RM.Thaji RK.Bergman RG.Ellman JA. Org. Lett. 2006, 8: 1745 -
1e
Fernandez LS.Buchanan MS.Carroll AR.Feng YJ.Quinn RJ.Avery VM. Org. Lett. 2009, 11: 329 -
2a
Molander GA.Schmitt MH. J. Org. Chem. 2000, 65: 3767 -
2b
Tanaka M.Ubukata M.Matsuo T.Yasue K.Matsumoto K.Kajimoto Y.Ogo T.Inaba T. Org. Lett. 2007, 9: 3331 -
3a
Flitsch W.Lubisch W. Chem. Ber. 1984, 117: 1424 -
3b
Padwa A.Fryxell GE.Gasdaska JR.Venakatraman MK.Wong GS. J. Org. Chem. 1989, 54: 644 -
3c
Coleman RS.Chen W. Org. Lett. 2001, 3: 1141 -
3d
Miki Y.Hachiken H.Kawazoe A.Tsuzaki Y.Yanase N. Heterocycles 2001, 55: 1291 -
3e
Yavari I.Adib M.Sayahi MH. J. Chem. Soc., Perkin Trans. 1 2002, 1517 -
3f
Borah HN.Deb ML.Boruah RC.Bhuvan PJ. Tetrahedron lett. 2005, 46: 3391 -
3g
Abbiati G.Casoni A.Canevari V.Nava D.Rossi E. Org. Lett. 2006, 8: 4839 -
3h
Manian RDRS.Jayashankaran J.Raghunanthan R. Synlett 2007, 874 -
3i
Hong L.Sun W.Liu C.Wang L.Wang R. Chem. Eur. J. 2010, 16: 440 - For selected recent reviews, see:
-
4a
Yamamoto Y.Radhakrishnan U. Chem. Soc. Rev. 1999, 28: 199 -
4b
Lu X.Zhang C.Xu Z. Acc. Chem. Res. 2001, 34: 535 -
4c
Bates RW.Satcharoen V. Chem. Soc. Rev. 2002, 31: 12 -
4d
Wei L.-L.Xiong H.Hsung RP. Acc. Chem. Res. 2003, 36: 773 -
4e
Ma S. Acc. Chem. Res. 2003, 36: 701 -
4f
Hoffmann-Röder A.Krause N. Angew. Chem. Int. Ed. 2004, 43: 1196 -
4g
Modern
Allene Chemistry
Krause N.Hashmi ASK. Wiley-VCH; Weinheim: 2004. -
4h
Brandsma L. Synthesis of Acetylenes, Allenes and Cumulenes: Methods and Techniques Elsevier; Oxford: 2004. -
4i
Ma S. Chem. Rev. 2005, 105: 2829 -
4j
Nair V.Menon RS.Sreekanth AR.Abhilash N.Biju AT. Acc. Chem. Res. 2006, 39: 520 -
4k
Ma S. Aldrichimica Acta 2007, 40: 91 -
4l
Pacheco MC.Purser S.Gouverneur V. Chem. Rev. 2008, 108: 1943 -
4m
Brasholz M.Reissig H.-U.Zimmer R. Acc. Chem. Res. 2009, 42: 45 -
4n
Ma S. Acc. Chem. Res. 2009, 42: 1679 -
4o
Deagostino A.Prandi C.Tabasso S.Venturello P. Molecules 2010, 15: 2667 -
5a
Chakravarty M.Kumara Swamy KC. J. Org. Chem. 2006, 71: 9128 -
5b
Kumara Swamy KC.Balaraman E.Satish Kumar N. Tetrahedron 2006, 62: 10152 -
5c
Chakravarty M.Kumara Swamy KC. Synthesis 2007, 3171 -
5d
Yu F.Lian X.Ma S. Org. Lett. 2007, 9: 1703 -
5e
Bravo-Altamirano K.Abrunhosa-Thomas I.Montchamp J.-L. J. Org. Chem. 2008, 73: 2292 -
5f
Panossian A.Fleury-Bregeot N.Marinetti A. Eur. J. Org. Chem. 2008, 3826 -
5g
Chakravarty M.Bhuvan Kumar NN.Sajna KV.Kumara Swamy KC. Eur. J. Org. Chem. 2008, 4500 -
5h
Brady PB.Morris EM.Fenton OS.Sculimbrene BR. Tetrahedron Lett. 2009, 50: 975 -
5i
Hirata Y.Inui T.Nakao Y.Hiyama T. J. Am. Chem. Soc. 2009, 131: 6624 -
5j
Li W.Shi M. Eur. J. Org. Chem. 2009, 270 -
5k
Zhou C.Fang Z.Fu C.Ma S. J. Org. Chem. 2009, 74: 2887 -
5l
Phani Pavan M.Chakravarty M.Kumara Swamy KC. Eur. J. Org. Chem. 2009, 5927 -
5m
Sajna KV.Kotikalapudi R.Chakravarty M.Bhuvan Kumar NN.Kumara Swamy KC. J. Org. Chem. 2011, 76: 920 - For reactions of allenic esters and ketones with salicyl N-tosylimines or aldehydes, see:
-
6a
Shi Y.-L.Shi M. Org. Lett. 2005, 7: 3057 -
6b
Zhao G.-L.Shi Y.-L.Shi M. Org. Lett. 2005, 7: 4527 -
6c
Shi M.Dai L.-Z.Shi Y.-L.Zhao G.-L. Adv. Synth. Catal. 2006, 348: 967 -
6d
Dai L.-Z.Shi Y.-L.Zhao G.-L.Shi M. Chem. Eur. J. 2007, 13: 3701 -
6e
Meng X.Huang Y.Chen R. Org. Lett. 2009, 11: 137 -
6f
Meng X.Huang Y.Zhao H.Xie P.Ma J.Chen R. Org. Lett. 2009, 11: 991 -
6g
Sun Y.-W.Guan X.-Y.Shi M. Org. Lett. 2010, 12: 5664 - 7 In our earlier work on salicylaldehydes
we faced some difficulties while using K2CO3 as
the base, although yields were very good, see:
Bhuvan Kumar NN.Nagarjuna Reddy M.Kumara Swamy KC. J. Org. Chem. 2009, 74: 5395 - 8
Majo VJ.Perumal PT. J. Org. Chem. 1996, 61: 6523 -
9a
Guillemin JC.Savignac P.Denis JM. Inorg. Chem. 1991, 30: 2170 -
9b
Iorga B.Eymery F.Carmichael D.Savignac P. Eur. J. Org. Chem. 2000, 3103 -
9c
Bhuvan Kumar NN.Chakravarty M.Satish Kumar N.Sajna KV.Kumara Swamy KC. J. Chem. Sci. 2009, 121: 23 - 10 Allenes 1d-f, 3a and 3b are new, but were prepared by using described
procedures.9,¹¹ See also:
Phani Pavan M. Dissertation University of Hyderabad; India: 2010. -
11a
Lang RW.Hansen H.-J. Org. Synth., Coll. Vol. VII John Wiley & Sons; London: 1990. p.232 -
11b
Ma S.Jiao N.Zhao S.Hou H. J. Org. Chem. 2002, 67: 2837 -
11c
Scheufler F.Maier ME. Eur. J. Org. Chem. 2000, 3945 - X-ray data for compounds 11 (CCDC 806280) and 12 (CCDC 806281) were collected on OXFORD diffractometer using Mo-Kα (λ = 0.71073 Å) radiation. The structures were solved and refined by standard methods, see:
-
13a
Sheldrick GM. SADABS, Siemens Area Detector Absorption Correction University of Göttingen; Germany: 1996. -
13b
Sheldrick GM. SHELX-97: A program for crystal structure solution and refinement University of Göttingen; Germany: 1997. -
13c
Sheldrick GM. SHELXTL NT Crystal Structure Analysis Package Version 5: Bruker AXS Analytical X-ray System; WI (USA): 1999. - 14 The requirement for a good electron-withdrawing substituent
to increase the reactivity of the indole has been reported, see:
Pintori DG.Greaney MF. J. Am. Chem. Soc. 2011, 133: 1209
References and Notes
Representative procedure for the preparation
of pyrrolo-indole 5: To the allene (0.200 g, 0.76 mmol), 3-chloro-2-formylindole4 (4; 0.176 g, 98 mmol) and K2CO3 (0.021
g, 0.15 mmol) in a 25 mL round-bottomed flask, was added PEG-400
(2 mL) and the contents were heated at 90 ˚C for 4 h.
The reaction mixture was quenched with H2O (5 mL) and
extracted with CH2Cl2 (3 × 25
mL). The whole organic layer was washed with H2O (3 × 25
mL), dried (Na2SO4), filtered, concentrated,
and the products were isolated by column chromatography (hexane-EtOAc,
1:4) on silica gel. Yield: 0.25 g (74%); mp 210-214 ˚C.
IR (KBr): 3316, 1634, 1601, 1443, 1327, 1308, 1061 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 0.68
(s, 3 H), 0.97 (s, 3 H), 3.53-3.56 (m,
1 H), 3.67-3.70 (m, 1 H), 3.95-4.00
(m, 2 H), 4.07-4.16 (m, 2 H), 5.43-5.47
(2 H), 6.64-7.45 (m, 9 H). ¹³C
NMR (100 MHz, CDCl3 + 5%MeOH): δ = 20.7,
21.3, 32.1, 62.4, 75.7, 76.1, 105.3 (d, J
P-C = 190.4 Hz),
114.5, 118.0, 122.3, 123.5, 128.2, 128.7, 131.0, 131.3, 131.7, 135.6,
142.0, 150.9 (d, J
P-C = 27.3 Hz). ³¹P
NMR (160 MHz, CDCl3): δ = 15.1.
LC/MS:
m/z = 442 [M - 2]+,
444 [M]+. Anal. Calcd for C23H23ClNO4P:
C, 62.24; H, 5.22; N, 3.16. Found: C, 62.35; H, 5.28; N, 3.22. Spectroscopic
and analytical data for the remaining pyrroloindoles 6-14 are given in the Supporting Information