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Synthesis 2012(4): 513-526  
DOI: 10.1055/s-0031-1289679
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

Bicyclo[3.2.0]heptane-Based Enamides by Ru/PNNP-Catalyzed Enantioselective Ficini Reactions: Scope and Application in Ligand Design

Christoph Schotes, Raphael Bigler, Antonio Mezzetti*
Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland
Fax: +41(44)6321310; e-Mail: mezzetti@inorg.chem.ethz.ch;
Further Information

Publication History

Received 9 December 2011
Publication Date:
30 January 2012 (online)

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Abstract

Double chloride abstraction from [RuCl2(PNNP)] [PNNP­ = (S,S)-N,N′-bis[o-(diphenylphosphino)benzylidene]cyclohexane-1,2-diamine] gives the elusive dicationic adduct [Ru(OEt)2(PNNP)]²+ which catalyzes the [2+2] cycloaddition of cyclic alkylidene β-keto esters with a variety of ynamides to produce bicyclo[3.2.0]heptane-based enamides with high yields and enan­tioselectivity. The structural features of these products are discussed and selected examples are converted into highly modular diene, phosphite-alkene, and diphosphite derivatives, which were tested as bidentate ligands with Rh(I), Ir(I), and Pd(II).

Key words

asymmetric catalysis - biaryls - cycloaddition - bicyclic compounds - ligands - phosphorus - ruthenium

    References

  • 1a Evano G. Coste A. Jouvin K. Angew. Chem. Int. Ed.  2010,  49:  2840 
    Google Scholar
  • 1b DeKorver KA. Li H. Lohse AG. Hayashi R. Lu Z. Zhang Y. Hsung RP. Chem. Rev.  2010,  110:  5064 
    Google Scholar
  • 2a Zhang Y. Hsung RP. Tracey MR. Kurtz KCM. Vera EL. Org. Lett.  2004,  6:  1151 
    Google Scholar
  • 2b Hamada T. Ye X. Stahl SS. J. Am. Chem. Soc.  2008,  130:  833 
    Google Scholar
  • 2c Coste A. Karthikeyan G. Couty F. Evano G. Angew. Chem. Int. Ed.  2009,  48:  4381 
    Google Scholar
  • 2d Jia W. Jiao N. Org. Lett.  2010,  12:  2000 
    Google Scholar
  • 2e Jouvin K. Couty F. Evano G. Org. Lett.  2010,  12:  3272 
    Google Scholar
  • 3a Ficini J. Krief A. Tetrahedron Lett.  1969,  10:  1431 
    Google Scholar
  • 3b Ficini J. Touzin AM. Tetrahedron Lett.  1972,  13:  2093 
    Google Scholar
  • 3c Ficini J. Touzin AM. Tetrahedron Lett.  1972,  13:  2097 
    Google Scholar
  • 3d Ficini J. Touzin AM. Tetrahedron Lett.  1974,  15:  1447 
    Google Scholar
  • 3e Ficini J. Falou S. d’Angelo J. Tetrahedron Lett.  1977,  18:  1931 
    Google Scholar
  • 4 Ficini J. Tetrahedron  1976,  32:  1449 
    Google Scholar
  • 5 Schotes C. Mezzetti A. Angew. Chem. Int. Ed.  2011,  50:  3072 ; Angew. Chem. 2011, 123, 3128
    Google Scholar
  • 6 Li H. Hsung RP. DeKorver KA. Wei Y. Org. Lett.  2010,  12:  3780 
    Google Scholar
  • 7 Gao JX. Ikariya T. Noyori R. Organometallics  1996,  15:  1087 
    Google Scholar
  • 8 Althaus M. Becker C. Togni A. Mezzetti A. Organometallics  2007,  26:  5902 
    Google Scholar
  • 9 Toullec PY. Bonaccorsi C. Mezzetti A. Togni A. Proc. Natl. Acad. Sci. U.S.A.  2004,  101:  5810 
    Google Scholar
  • 10a Santoro F. Althaus M. Bonaccorsi C. Gischig S. Mezzetti A. Organometallics  2008,  27:  3866 
    Google Scholar
  • 10b Althaus M. Bonaccorsi C. Mezzetti A. Santoro F. Organometallics  2006,  25:  3108 
    Google Scholar
  • 10c Bonaccorsi C. Althaus M. Becker C. Togni A. Mezzetti A. Pure Appl. Chem.  2006,  78:  391 
    Google Scholar
  • 11a Schotes C. Mezzetti A. J. Am. Chem. Soc.  2010,  132:  3652 
    Google Scholar
  • 11b Schotes C. Mezzetti A. Chimia  2011,  65:  231 
    Google Scholar
  • 11c Schotes C. Althaus M. Aardoom R. Mezzetti A.
    J. Am. Chem. Soc.  2012,  134:  1331 
    Google Scholar
  • 12 Defieber C. Grützmacher H. Carreira EM. Angew. Chem. Int. Ed.  2008,  47:  4482 
    Google Scholar
  • 13a Hayashi T. Ueyama K. Tokunaga N. Yoshida K.
    J. Am. Chem. Soc.  2003,  125:  11508 
    Google Scholar
  • 13b Berthon-Gelloz G. Hayashi T. J. Org. Chem.  2006,  71:  8957 
    Google Scholar
  • 14a Fischer C. Defieber C. Suzuki T. Carreira EM. J. Am. Chem. Soc.  2004,  126:  1628 
    Google Scholar
  • 14b Defieber C. Paquin J.-F. Serna S. Carreira EM. Org. Lett.  2004,  6:  3873 
    Google Scholar
  • 16a Okamoto K. Hayashi T. Rawal VH. Org. Lett.  2008,  10:  4387 
    Google Scholar
  • 16b Nishimura T. Nagaosa M. Hayashi T. Chem. Lett.  2008,  37:  860 
    Google Scholar
  • 17 Schotes C. Mezzetti A. J. Org. Chem.  2011,  76:  5862 
    Google Scholar
  • 18 Recent review article: van Leeuwen PWNM. Kamer PCJ. Claver C. Pàmies O. Diéguez M. Chem. Rev.  2011,  111:  2077 
    Google Scholar
  • 19 Recent review article: Wassenaar J. Reek JNH. Org. Biomol. Chem.  2011,  9:  1704 
    Google Scholar
  • 20a Maire P. Deblon S. Breher F. Geier J. Böhler C. Rüegger H. Schönberg H. Grützmacher H. Chem. Eur. J.  2004,  10:  4198 
    Google Scholar
  • 20b Piras E. Läng F. Rüegger H. Stein D. Wörle M. Grützmacher H. Chem. Eur. J.  2006,  12:  5849 
    Google Scholar
  • 20c Shintani R. Duan W.-L. Nagano T. Okada A. Hayashi T. Angew. Chem. Int. Ed.  2005,  44:  4611 
    Google Scholar
  • 20d Shintani R. Duan W.-L. Okamoto K. Hayashi T. Tetrahedron: Asymmetry  2005,  16:  3400 
    Google Scholar
  • 20e Duan W.-L. Iwamura H. Shintani R. Hayashi T. J. Am. Chem. Soc.  2007,  129:  2130 
    Google Scholar
  • 20f Cao Z. Liu Y. Liu Z. Feng X. Du H. Org. Lett.  2011,  13:  9 
    Google Scholar
  • 20g Kasák P. Arion VB. Widhalm M. Tetrahedron: Asymmetry  2006,  17:  3084 
    Google Scholar
  • 20h Stemmler RT. Bolm C. Synlett  2007,  1365 
    Google Scholar
  • 20i Štěpnička P. Cisařová I. Inorg. Chem.  2006,  45:  8785 
    Google Scholar
  • 20j Š těpnička P. Lamač M. Cisařová I. J. Organomet. Chem.  2008,  693:  446 
    Google Scholar
  • 20k Liu Z. Du H. Org. Lett.  2010,  12:  3054 
    Google Scholar
  • 21 Minuth T. Boysen MMK. Org. Lett.  2009,  11:  4212 
    Google Scholar
  • 22a Defieber C. Ariger MA. Moriel P. Carreira EM. Angew. Chem. Int. Ed.  2007,  46:  3139 
    Google Scholar
  • 22b Roggen M. Carreira EM. Angew. Chem. Int. Ed.  2011,  50:  5568 
    Google Scholar
  • 22c Shintani R. Narui R. Tsutsumi Y. Hayashi S. Hayashi T. Chem. Commun.  2011,  47:  6123 
    Google Scholar
  • 24 Gennari C. Monti C. Piarulli U. Pure Appl. Chem.  2006,  78:  303 
    Google Scholar
  • 25 Mikami K. Aikawa K. Yusa Y. Jodry JJ. Yamanaka M. Synlett  2002,  1561 
    Google Scholar
  • 27a

    At difference, P,P-coupling has been observed in other diphosphites featuring inequivalent P-donors,²7b which has been interpreted as through-space coupling

  • 27b Buisman GJH. van der Veen LA. Klootwijk A. de Lange WGJ. Kamer PCJ. van Leeuwen PWNM. Vogt D. Organometallics  1997,  16:  2929 
    Google Scholar
  • 29 Diéguez M. Ruiz A. Claver C. Dalton Trans.  2003,  2957 
    Google Scholar
  • 30a Riddell N. Villeneuve K. Tam W. Org. Lett.  2005,  7:  3681 
    Google Scholar
  • 30b Villeneuve K. Riddell N. Tam W. Tetrahedron  2006,  62:  3823 
    Google Scholar
  • 31 For investigations on monocationic Ru/PNNP complexes, see: Schotes C. Ranocchiari M. Mezzetti A. Organometallics  2011,  30:  3596 
    Google Scholar
  • 32 Baker R. Selwood DL. Swain CJ. Webster NMH. J. Chem. Soc., Perkin Trans. 1  1988,  471 
    Google Scholar
  • 33 Johnson DC. Widlanski TS. J. Org. Chem.  2003,  68:  5300 
    Google Scholar
  • 34 Miura K. Saito H. Fujisawa N. Wang D. Nishikori H. Hosomi A. Org. Lett.  2001,  3:  4055 
    Google Scholar
  • 35 Swamy KCK. Kumaraswamy S. Kumar KS. Muthiah C. Tetrahedron Lett.  2005,  46:  3347 
    Google Scholar
  • 36 Vallée C. Chauvin Y. Basset J.-M. Santini CC. Galland J.-C. Adv. Synth. Catal.  2005,  347:  1835 
    Google Scholar
  • 37a van der Vlugt JI. Hewat AC. Neto S. Sablong R. Mills AM. Lutz M. Spek AL. Müller C. Vogt D. Adv. Synth. Catal.  2004,  346:  993 
    Google Scholar
  • 37b Pastor SD. Shum SPR. Rodebaugh K. Debellis AD. Clarke FH. Helv. Chim. Acta  1993,  76:  900 
    Google Scholar
  • 38a Leung W. Cosway R. Jones RHV. McCann H. Wills M. J. Chem. Soc., Perkin Trans. 1  2001,  2588 
    Google Scholar
  • 38b Watson IDG. Styler SA. Yudin AK. J. Am. Chem. Soc.  2004,  126:  5086 
    Google Scholar
15

Also, an attempted acetal protection of 5a under various standard conditions failed, most probably due to the congested spatial arrangement.

23

Nucleophilic substitution reactions on Ph2PCl with 6a and Et3N or NaH as a base were attempted. However, no conversion was detected by TLC and, after aqueous workup, by NMR after 24 h at r.t.

26

X-ray crystallography: CCDC-856610 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at http://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
e-mail: deposit@ccdc.cam.ac.uk]. Although the starting Ficini product 5p was enantiomerically enriched (74% ee), 8d crystallized from hot hexane as a racemate in the centrosymmetric P21/c space group. See the Supporting Information for selected distances and angles.

28

See Supporting Information for additional studies with ligand 10b and [Rh(acac)(C2H4)2] as metal precursor.