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

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 
• 1b DeKorver KA. Li H. Lohse AG. Hayashi R. Lu Z. Zhang Y. Hsung RP. Chem. Rev.  2010,  110:  5064 
• 2a Zhang Y. Hsung RP. Tracey MR. Kurtz KCM. Vera EL. Org. Lett.  2004,  6:  1151 
• 2b Hamada T. Ye X. Stahl SS. J. Am. Chem. Soc.  2008,  130:  833 
• 2c Coste A. Karthikeyan G. Couty F. Evano G. Angew. Chem. Int. Ed.  2009,  48:  4381 
• 2d Jia W. Jiao N. Org. Lett.  2010,  12:  2000 
• 2e Jouvin K. Couty F. Evano G. Org. Lett.  2010,  12:  3272 
• 3a Ficini J. Krief A. Tetrahedron Lett.  1969,  10:  1431 
• 3b Ficini J. Touzin AM. Tetrahedron Lett.  1972,  13:  2093 
• 3c Ficini J. Touzin AM. Tetrahedron Lett.  1972,  13:  2097 
• 3d Ficini J. Touzin AM. Tetrahedron Lett.  1974,  15:  1447 
• 3e Ficini J. Falou S. d’Angelo J. Tetrahedron Lett.  1977,  18:  1931 
• 4 Ficini J. Tetrahedron  1976,  32:  1449 
• 5 Schotes C. Mezzetti A. Angew. Chem. Int. Ed.  2011,  50:  3072 ; Angew. Chem. 2011, 123, 3128
• 6 Li H. Hsung RP. DeKorver KA. Wei Y. Org. Lett.  2010,  12:  3780 
• 7 Gao JX. Ikariya T. Noyori R. Organometallics  1996,  15:  1087 
• 8 Althaus M. Becker C. Togni A. Mezzetti A. Organometallics  2007,  26:  5902 
• 9 Toullec PY. Bonaccorsi C. Mezzetti A. Togni A. Proc. Natl. Acad. Sci. U.S.A.  2004,  101:  5810 
• 10a Santoro F. Althaus M. Bonaccorsi C. Gischig S. Mezzetti A. Organometallics  2008,  27:  3866 
• 10b Althaus M. Bonaccorsi C. Mezzetti A. Santoro F. Organometallics  2006,  25:  3108 
• 10c Bonaccorsi C. Althaus M. Becker C. Togni A. Mezzetti A. Pure Appl. Chem.  2006,  78:  391 
• 11a Schotes C. Mezzetti A. J. Am. Chem. Soc.  2010,  132:  3652 
• 11b Schotes C. Mezzetti A. Chimia  2011,  65:  231 
• 11c Schotes C. Althaus M. Aardoom R. Mezzetti A.
  J. Am. Chem. Soc.  2012,  134:  1331 
• 12 Defieber C. Grützmacher H. Carreira EM. Angew. Chem. Int. Ed.  2008,  47:  4482 
• 13a Hayashi T. Ueyama K. Tokunaga N. Yoshida K.
  J. Am. Chem. Soc.  2003,  125:  11508 
• 13b Berthon-Gelloz G. Hayashi T. J. Org. Chem.  2006,  71:  8957 
• 14a Fischer C. Defieber C. Suzuki T. Carreira EM. J. Am. Chem. Soc.  2004,  126:  1628 
• 14b Defieber C. Paquin J.-F. Serna S. Carreira EM. Org. Lett.  2004,  6:  3873 
• 16a Okamoto K. Hayashi T. Rawal VH. Org. Lett.  2008,  10:  4387 
• 16b Nishimura T. Nagaosa M. Hayashi T. Chem. Lett.  2008,  37:  860 
• 17 Schotes C. Mezzetti A. J. Org. Chem.  2011,  76:  5862 
• 18 Recent review article: van Leeuwen PWNM. Kamer PCJ. Claver C. Pàmies O. Diéguez M. Chem. Rev.  2011,  111:  2077 
• 19 Recent review article: Wassenaar J. Reek JNH. Org. Biomol. Chem.  2011,  9:  1704 
• 20a Maire P. Deblon S. Breher F. Geier J. Böhler C. Rüegger H. Schönberg H. Grützmacher H. Chem. Eur. J.  2004,  10:  4198 
• 20b Piras E. Läng F. Rüegger H. Stein D. Wörle M. Grützmacher H. Chem. Eur. J.  2006,  12:  5849 
• 20c Shintani R. Duan W.-L. Nagano T. Okada A. Hayashi T. Angew. Chem. Int. Ed.  2005,  44:  4611 
• 20d Shintani R. Duan W.-L. Okamoto K. Hayashi T. Tetrahedron: Asymmetry  2005,  16:  3400 
• 20e Duan W.-L. Iwamura H. Shintani R. Hayashi T. J. Am. Chem. Soc.  2007,  129:  2130 
• 20f Cao Z. Liu Y. Liu Z. Feng X. Du H. Org. Lett.  2011,  13:  9 
• 20g Kasák P. Arion VB. Widhalm M. Tetrahedron: Asymmetry  2006,  17:  3084 
• 20h Stemmler RT. Bolm C. Synlett  2007,  1365 
• 20i Štěpnička P. Cisařová I. Inorg. Chem.  2006,  45:  8785 
• 20j Š těpnička P. Lamač M. Cisařová I. J. Organomet. Chem.  2008,  693:  446 
• 20k Liu Z. Du H. Org. Lett.  2010,  12:  3054 
• 21 Minuth T. Boysen MMK. Org. Lett.  2009,  11:  4212 
• 22a Defieber C. Ariger MA. Moriel P. Carreira EM. Angew. Chem. Int. Ed.  2007,  46:  3139 
• 22b Roggen M. Carreira EM. Angew. Chem. Int. Ed.  2011,  50:  5568 
• 22c Shintani R. Narui R. Tsutsumi Y. Hayashi S. Hayashi T. Chem. Commun.  2011,  47:  6123 
• 24 Gennari C. Monti C. Piarulli U. Pure Appl. Chem.  2006,  78:  303 
• 25 Mikami K. Aikawa K. Yusa Y. Jodry JJ. Yamanaka M. Synlett  2002,  1561 
• 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 
• 29 Diéguez M. Ruiz A. Claver C. Dalton Trans.  2003,  2957 
• 30a Riddell N. Villeneuve K. Tam W. Org. Lett.  2005,  7:  3681 
• 30b Villeneuve K. Riddell N. Tam W. Tetrahedron  2006,  62:  3823 
• 31 For investigations on monocationic Ru/PNNP complexes, see: Schotes C. Ranocchiari M. Mezzetti A. Organometallics  2011,  30:  3596 
• 32 Baker R. Selwood DL. Swain CJ. Webster NMH. J. Chem. Soc., Perkin Trans. 1  1988,  471 
• 33 Johnson DC. Widlanski TS. J. Org. Chem.  2003,  68:  5300 
• 34 Miura K. Saito H. Fujisawa N. Wang D. Nishikori H. Hosomi A. Org. Lett.  2001,  3:  4055 
• 35 Swamy KCK. Kumaraswamy S. Kumar KS. Muthiah C. Tetrahedron Lett.  2005,  46:  3347 
• 36 Vallée C. Chauvin Y. Basset J.-M. Santini CC. Galland J.-C. Adv. Synth. Catal.  2005,  347:  1835 
• 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 
• 37b Pastor SD. Shum SPR. Rodebaugh K. Debellis AD. Clarke FH. Helv. Chim. Acta  1993,  76:  900 
• 38a Leung W. Cosway R. Jones RHV. McCann H. Wills M. J. Chem. Soc., Perkin Trans. 1  2001,  2588 
• 38b Watson IDG. Styler SA. Yudin AK. J. Am. Chem. Soc.  2004,  126:  5086 

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: [phone]; or
e-mail: [e-mail]]. 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.