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Synthesis 2011(10): 1587-1594
DOI: 10.1055/s-0030-1260012
DOI: 10.1055/s-0030-1260012
PAPER
© Georg Thieme Verlag
Stuttgart ˙ New York
Diversity-Oriented Silver(I)-Mediated Synthesis of Spiro-2-aminoimidazoles
Further Information
Received
21 February 2011
Publication Date:
19 April 2011 (online)
Publication History
Publication Date:
19 April 2011 (online)
Abstract
A diversity-oriented protocol giving access to a novel class of spiro-cyclic guanidine derivatives is described. The copper(I)-catalyzed, three-component coupling of a ketone, an alkyne and a primary amine (KA²-coupling) provides the required secondary propargylamines and assures the generation of diversity. The key step of the protocol, a silver(I)-mediated tandem guanylation of secondary propargylamines followed by an intramolecular heterocyclization, provides the target bis-Boc-protected-2-iminoimidazolines spiro-fused with a five-, six- or seven-membered (heterocyclic) ring, which could, in most cases, be further deprotected to the spiro-2-aminoimidazoles.
Key words
2-aminoimidazoles - spiro compounds - tandem reaction - ring closure - silver
-
1a
Berlinck RGS.Burtoloso ACB.Trindade-Silva AE.Romminger S.Morais RP.Bandeira K.Mizuno CM. Nat. Prod. Rep. 2010, 27: 1871 -
1b
Berlinck RGS.Burtoloso ACB.Kossuga MH. Nat. Prod. Rep. 2008, 25: 919 -
1c
Berlinck RGS.Kossuga MH. Nat. Prod. Rep. 2005, 22: 516 -
1d
Berlinck RGS. Nat. Prod. Rep. 2002, 19: 617 ; and references cited therein - For anti-biofilm activity of 2-aminoimidazoles, see:
-
2a
Huigens RW.Richards JJ.Parise G.Ballard TE.Zeng W.Deora R.Melander C. J. Am. Chem. Soc. 2007, 129: 6966 -
2b
Rogers SA.Melander C. Angew. Chem. Int. Ed. 2008, 47: 5229 ; Angew. Chem. 2008, 120, 5307 -
2c
Ballard TE.Richards JJ.Wolf AL.Melander C. Chem. Eur. J. 2008, 14: 10745 -
3a
Malamas MS.Erdei J.Gunawan I.Turner J.Hu Y.Wagner E.Fan K.Chopra R.Olland A.Bard J.Jacobsen S.Magolda RL.Pangalos M.Robichaud AJ. J. Med. Chem. 2010, 53: 1146 -
3b
Malamas MS.Erdei J.Gunawan I.Barnes K.Johnson M.Hui Y.Turner J.Hu Y.Wagner E.Fan K.Olland A.Bard J.Robichaud AJ. J. Med. Chem. 2009, 52: 6314 -
4a
Coleman RS.Campbell EL.Carper DJ. Org. Lett. 2009, 11: 2133 -
4b
Nodwell M.Pereira A.Riffell JL.Zimmermann C.Patrick BO.Roberge M.Andersen RJ. J. Org. Chem. 2009, 74: 995 -
5a
Jin Z. Nat. Prod. Rep. 2003, 20: 584 -
5b
Jin Z. Nat. Prod. Rep. 2005, 22: 196 -
5c
Jin Z. Nat. Prod. Rep. 2006, 23: 464 -
5d
Jin Z. Nat. Prod. Rep. 2009, 26: 382 -
5e
Weinreb SM. Nat. Prod. Rep. 2007, 24: 931 -
5f
Sullivan JD.Giles RL.Looper RE. Curr. Bioact. Compd. 2009, 5: 39 -
5g
Hoffmann H.Lindel T. Synthesis 2003, 175 -
5h
Koswatta PB.Lovely CJ. Nat. Prod. Rep. 2010, 28: 511 ; and references cited therein -
6a
Dunbar DC.Rimoldi JM.Clark AM.Kelly M.Hamann MT. Tetrahedron 2000, 56: 8795 -
6b
Crews P.Clark DP.Tenney K. J. Nat. Prod. 2003, 66: 177 -
6c
Hassan W.Edrada R.Ebel R.Wray V.Berg A.Van Soest R.Wiryowidagdo S.Proksch P. J. Nat. Prod. 2004, 67: 817 -
7a
Fu X.Barnes JR.Do T.Schmitz FJ. J. Nat. Prod. 1997, 60: 497 -
7b
Gross H.Kehraus S.König GM.Woerheide G.Wright AD. J. Nat. Prod. 2002, 65: 1190 -
8a
Carmely S.Kashman Y. Tetrahedron Lett. 1987, 28: 3003 -
8b
Carmely S.Ilan M.Kashman Y. Tetrahedron 1989, 45: 2193 - 9
Fu X.Schmitz FJ.Tanner RS.Kelly-Borges M.
J. Nat. Prod. 1998, 61: 384 -
10a
Akee RK.Carroll TR.Yoshida WY.Scheuer PJ.Stout TJ.Clardy J. J. Org. Chem. 1990, 55: 1944 -
10b
Carroll AR.Bowden BF.Coll JC. Aust. J. Chem. 1993, 46: 1229 -
10c
Mancini I.Guella G.Debitus C.Pietra F. Helv. Chim. Acta 1995, 78: 1178 -
10d
Plubrukarn A.Smith D.Cramer R.Davidson B. J. Nat. Prod. 1997, 60: 712 - 11
Edrada RA.Stessman CC.Crews P. J. Nat. Prod. 2003, 66: 939 - For original isolation, see:
-
12a
Kinnel RB.Gehrken HP.Scheuer PJ. J. Am. Chem. Soc. 1993, 115: 3376 -
12b
Kinnel RB.Gehrken HP.Swali R.Skoropowski G.Scheuer PJ. J. Org. Chem. 1998, 63: 3281 -
12c For structural reassignment,
see:
Buchanan MS.Carroll AR.Quinn RJ. Tetrahedron Lett. 2007, 48: 4573 -
12d For total synthesis, see:
Seiple IB.Su S.Young IS.Lewis CA.Yamaguchi J.Baran PS. Angew. Chem. Int. Ed. 2010, 49: 1095 ; and references cited therein - 13 For a review on the synthesis of
alkaloids from the Oroidin family, see:
Arndt HD.Riedrich M. Angew. Chem. Int. Ed. 2008, 47: 4785 -
14a
Sivappa R.Koswatta P.Lovely CJ. Tetrahedron Lett. 2007, 48: 5771 -
14b
Sivappa R.Hernandez NM.He Y.Lovely CJ. Org. Lett. 2007, 9: 3861 -
14c
Lovely CJ.Du H.He Y.Dias HVR. Org. Lett. 2004, 6: 735 - 15
Iwagawa T.Miyazaki M.Okamura H.Nakatani M.Doe M.Takemura K. Tetrahedron Lett. 2003, 44: 2533 - 16
Capon RJ.Rooney F.Murray LM.Collins E.Sim ATR.Rostas JAP.Butler MS.Carroll AR. J. Nat. Prod. 1998, 61: 660 - For synthetic efforts towards dragmacidin E, see:
-
17a
Feldman KS.Ngernmeesri P. Org. Lett. 2005, 7: 5449 -
17b
Huntley RJ.Funk RL. Org. Lett. 2006, 8: 4775 -
17c
Feldman KS.Ngernmeesri P. Org. Lett. 2010, 12: 4502 - 18
Giles RL.Sullivan JD.Steiner AM.Looper RE. Angew. Chem. Int. Ed. 2009, 48: 3116 -
19a
Ermolat’ev DS.Babaev EV.Van der Eycken EV. Org. Lett. 2006, 8: 5781 -
19b
Ermolat’ev DS.Alifanov VL.Rybakov VB.Babaev EV.Van der Eycken EV. Synthesis 2008, 2083 -
19c
Ermolat’ev DS.Van der Eycken EV. J. Org. Chem. 2008, 73: 6691 -
19d
Ermolat’ev DS.Svidritzky EP.Babaev EV.Van der Eycken E. Tetrahedron Lett. 2009, 50: 5218 -
19e
Modha SG.Mehta VP.Ermolat’ev DS.Balzarini J.Van Hecke K.Van Meervelt L.Van der Eycken E. Mol. Diversity 2010, 14: 767 - 20
Ermolat’ev DS.Bariwal JB.Steenackers HPL.De Keersmaecker SCJ.Van der Eycken EV. Angew. Chem. Int. Ed. 2010, 49: 9465 - 21
Ermolat’ev DS. PhD Thesis Katholieke Universiteit Leuven; Belgium: 2008. - 22 For the synthesis of secondary propargylamines,
see:
Bariwal JB.Ermolat’ev DS.Van der Eycken EV. Chem. Eur. J. 2010, 16: 3281 - 23 For a description of the KA²-coupling,
see:
Pereshivko OP.Peshkov VA.Van der Eycken EV. Org. Lett. 2010, 12: 2638 - 24 During the preparation of this manuscript,
the rhodium(II)-catalyzed 6-endo-dig-selective
hydroamination of propargylguanidines was reported, see:
Gainer MJ.Bennett NR.Takahashi Y.Looper RE. Angew. Chem. Int. Ed. 2011, 50: 684 - 25 For the addition of lithium acetylides
and n-BuLi to six-membered ketimines,
see:
Ma Y.Lobkovsky E.Collum DB. J. Org. Chem. 2005, 70: 2335
References
Differences in R f values allow both minor and major products to be isolated through gradient-elution column chromatography.
27See Supporting Information for details.
28CCDC-801762 contains the supplementary crystallographic data for this paper and can be obtained free of charge via 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)336033; or deposit@ccdc.cam.ac.uk).