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DOI: 10.1055/s-0030-1260973
Regioselective Synthesis of Substituted Imidate N-[1-Methyleneisobenzofuran-3(1H)-ylidene]benzenamines via Palladium-Catalyzed Tandem Heteroannulation of o-(1-Alkynyl)benzamides with Iodobenzene
Publication History
Publication Date:
25 July 2011 (online)
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Abstract
A variety of substituted imidate N-[1-methyleneisobenzofuran-3(1H)-ylidene]benzenamines have been prepared in good to excellent yields by the palladium-catalyzed tandem heteroannulation of o-(1-alkynyl)benzamides with iodobenzene. The products obtained from this process were unusual substituted N-[isobenzofuran-3(1H)-ylidene]benzenamines. The tandem cyclization of readily available o-(1-alkynyl)benzamides and aryl iodides provided a powerful tool for the preparation of functionally substituted N-[isobenzofuran-3(1H)-ylidene]benzenamine compounds.
Keywords
isobenzofuran - o-(1-alkynyl)benzamide - iodobenzene - tandem - palladium catalysis
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- Supporting Information
-
1a
Tietze LF. Chem. Rev. 1996, 96: 115 -
1b
Malacria M. Chem. Rev. 1996, 96: 289 -
1c
Ikeda S.-I. Acc. Chem. Res. 2000, 33: 511 -
1d
Battistuzzi G.Cacchi S.Fabrizi G. Eur. J. Org. Chem. 2002, 2671 -
1e
Balme G.Bossharth E.Monteiro N. Eur. J. Org. Chem. 2003, 4101 -
1f
Luo F.-T.Wang R.-T. Tetrahedron Lett. 1991, 32: 7703 -
1g
Oh CH.Lim YM. Tetrahedron Lett. 2003, 44: 2670 -
2a
Ha Y.-H.Kang S.-K. Org. Lett. 2002, 4: 1143 -
2b
Ohno H.Miyamura K.Takeoka Y.Tanaka T. Angew. Chem. Int. Ed. 2003, 42: 2647 -
2c
Kneisel FF.Dochnahl M.Knochel P. Angew. Chem. Int. Ed. 2004, 43: 1017 -
2d
Kressierer CJ.Müller TJJ. Angew. Chem. Int. Ed. 2004, 43: 5997 -
2e
Zhu G.Zhang Z. Org. Lett. 2004, 6: 4041 -
2f
Zhu G.Tong X.Cheng J.Sun Y.Li D.Zhang Z. J. Org. Chem. 2005, 70: 1712 -
2g
Pinto A.Neuville L.Retailleau P.Zhu J. Org. Lett. 2006, 8: 4927 -
2h
Ishikura M.Takahashi N.Yamada K.Yanada R. Tetrahedron 2006, 62: 11580 -
3a
Larock RC. J. Organomet. Chem. 1999, 576: 111 -
3b
Nakamura I.Yamamoto Y. Chem. Rev. 2004, 104: 2127 -
3c
Zeni G.Larock RC. Chem. Rev. 2004, 104: 2285 -
3d
Alonso F.Beletskaya IP.Yus M. Chem. Rev. 2004, 104: 3079 -
3e
Cacchi S.Fabrizi G. Chem. Rev. 2005, 105: 2873 -
3f
Zeni G.Larock RC. Chem. Rev. 2006, 106: 4644 -
4a
Madin A.O’Donnell CJ.Oh T.Old DW.Overman LE.Sharp MJ. Angew. Chem. Int. Ed. 1999, 38: 2934 -
4b
Hynes J.Overman LE.Nasser T.Rucker PV. Tetrahedron Lett. 1998, 39: 4647 -
4c
Hong CY.Overman LE.Romero A. Tetrahedron Lett. 1997, 38: 8439 -
4d
Wu GG.Wong YS.Poirier M. Org. Lett. 1999, 1: 745 -
4e
Smith GB.Dezeny GC.Hughes DL.King AO.Verhoeven TR. J. Org. Chem. 1994, 59: 8151 -
5a
Pedrosa R.Sayalero S.Vicente M. Tetrahedron 2006, 62: 10400 -
5b
Zhu XZ.Li X.-Y.Liu J. Eur. J. Pharmacol. 2004, 500: 221 -
5c
Rao YS. Chem. Rev. 1976, 76: 625 -
5d
Mukhopadhyay R.Kundu NG. Tetrahedron 2001, 57: 9475 -
6a
Baldwin JE.Bair KW. Tetrahedron Lett. 1978, 19: 2559 -
6b
Kim KS.Spatz MW.Johnson F. Tetrahedron Lett. 1979, 20: 331 -
6c
Pahari P.Senapati B.Mal D. Tetrahedron Lett. 2004, 45: 5109 -
6d
Mal D.Pahari P.De S R. Tetrahedron 2007, 63: 11781 -
7a
Landge SM.Berryman M.Török B. Tetrahedron Lett. 2008, 49: 4505 -
7b
Paradkar MV.Gadre SY.Pujari TA.Khandekar PP.Kumbhar VB. Synth. Commun. 2005, 35: 471 -
8a
Brotherton TK.Lynn JW. Chem. Rev. 1959, 59: 841 -
8b
Roger R.Neilson DG. Chem. Rev. 1961, 61: 179 -
9a
Grossman RB.Rasne RM. Org. Lett. 2001, 3: 4027 -
9b
Hamada Y.Hara O.Kawai A.Kohno Y.Shioiri T. Tetrahedron 1991, 47: 8635 -
10a
Bundgaard H.Larsen JD. J. Med. Chem. 1988, 31: 2066 -
10b
Kini GD.Robins RK.Avery TL. J. Med. Chem. 1989, 32: 1447 -
11a
Pinner A.Klein F. Ber. Dtsch. Chem. Ges. 1877, 10: 1889 -
11b
Pinner A.Klein F. Ber. Dtsch. Chem. Ges. 1878, 11: 1475 -
11c
Pinner A. Ber. Dtsch. Chem. Ges. 1883, 16: 1643 - 12
Kochi T.Ellman JA. J. Am. Chem. Soc. 2004, 126: 15652 - 13
Restituyo JA.Comstock LR.Petersen SG.Stringfellow T.Rajski SR. Org. Lett. 2003, 5: 4357 - 14
Schaefer FC.Peters GA. J. Org. Chem. 1961, 26: 412 -
15a
Yoo EJ.Bae I.Cho SH.Han H.Chang S. Org. Lett. 2006, 8: 1347 -
15b
Yoo EJ.Ahlquist M.Bae I.Sharpless KB.Fokin VV.Chang S. J. Org. Chem. 2008, 73: 5520 -
16a
Saluste CG.Crumpler S.Furber M.Whitby RJ. Tetrahedron Lett. 2004, 45: 6995 -
16b
Fernandez-Rivas C.Cardenas DJ.Martin-Matute B.Monge A.Gutierrez-Puebla E.Echavarren AM. Organometallics 2001, 20: 2998 -
17a
Yoshida H.Fukushima H.Ohshita J.Kunai A. Angew. Chem. Int. Ed. 2004, 43: 3935 -
17b
Yoshida H.Fukushima H.Morishita T.Ohshita J.Kunai A. Tetrahedron 2007, 63: 4793 - 18
Yao T.Larock RC. J. Org. Chem. 2005, 70: 1432 - 19
Xie Y.-X.Yan Z.-Y.Wang D.-Z.Wu L.-Y.Qian B.Liu X.-Y.Liang Y.-M. Eur. J. Org. Chem. 2009, 2283 -
22a
Guo L.-N.Duan X.-H.Bi H.-P.Liu X.-Y.Liang Y.-M. J. Org. Chem. 2006, 71: 3325 -
22b
Duan X.-H.Guo L.-N.Bi H.-P.Liu X.-Y.Liang Y.-M. Org. Lett. 2006, 8: 3053 -
22c
Bossharth E.Desbordes P.Monteiro N.Balme G. Org. Lett. 2003, 5: 2441 -
22d
Dai G.Larock RC. Org. Lett. 2001, 3: 4035 -
22e
Dai G.Larock RC. J. Org. Chem. 2003, 68: 920
References and Notes
General Procedure for the Preparation of N -[Isobenzo-furan-1 (3 H )-ylidene]benzenamine Compounds To a solution of o-(1-alkynyl)benzamides 1 (0.50 mmol) in MeCN (3.0 mL) was added 2,6-lutidine (1.00 mmol). The mixture was stirred for 10 min and Pd(PPh3)4 (5 mol%) and organic halides (0.60 mmol) were added. The resulting mixture was then heated under an argon atmosphere at refluxing temperature. When the reaction was considered complete, as determined by TLC analysis, the reaction mixture was cooled to r.t., quenched with a sat. aq solution of NH4Cl, and extracted with EtOAc. The combined organic extracts were washed with H2O and sat. brine. The organic layers were dried over Na2SO4 and filtered. The solvents were evaporated under reduced pressure. The residue was purified by chromatography on silica gel to afford the corresponding N-[1-(diphenylmethylene)isobenzofuran-3 (1H)-ylidene]benzenamine. Thus, starting with 1a (149 mg, 0.5 mmol) and iodobenzene 2a (122 mg, 0.6mmol), a yellowish solid product 4aa (273 mg, 73%) was isolated; mp 173-175 ˚C. ¹H NMR (300 MHz, CDCl3): δ = 6.24 (d, J = 8.0 Hz, 1 H), 7.14-7.29 (m, 5 H), 7.35-7.41 (m, 5 H), 7.48-7.52 (m, 7 H), 8.00 (d, J = 7.6 Hz, 1 H). ¹³C NMR (75 MHz, CDCl3): δ = 120.77, 123.27, 123.42, 124.02, 124.76, 127.50, 127.86, 128.38, 128.59, 129.24, 129.26, 129.86, 130.66, 130.82, 131.68, 136.67, 137.80, 137.90, 145.64, 145.77, 153.98. IR (neat): 3052, 2923, 1681, 1013, 755, 693 cm-¹. Anal. Calcd for C27H19NO: C, 86.84; H, 5.13; N, 3.75; O, 4.28. Found: C, 86.70; H, 5.06; N, 3.73; O, 4.35.
21The atomic coordinates for 4ac have been deposited at the Cambridge Crystallographic Data Centre (deposition number: CCDC 800275). The coordinates can be obtained on request from the Director Cambridge Crystallographic Data Centre. Postal Address: 12 Union Road, Cambridge CB2 1EZ, UK; Email: deposit@ccdc.cam.ac.uk; fax: +44 (1223) 336033; tel.: +44 (1223)762910.