Functional-Group Attachment and Interconversion at a Chiral [3]Ferrocenophane Framework

Abstract

Mannich condensation of 1,1′-diacetylferrocene with dimethylamine followed by catalytic hydrogenation gives the chiral α-dimethylamino[3]ferrocenophane. Both enantiomers are available by resolution. Directed ortho-lithiation/iodination yields the ortho-iodo-α-dimethylamino[3]ferrocenophane derivative, whose treatment with acetic anhydride and copper(I) oxide yielded the mono- and diacetoxy-functionalized derivatives. The ortho-phosphorylated α-dimethylamino systems (-PPh₂, -PCy₂) underwent exchange of the directing NMe₂ group with NH₂ by means of an ammonolysis reaction of the corresponding α-chloride derivatives, which in turn were obtained by treatment of the α-dimethylamino compounds with methylchloroformate. Starting from α-dimethyl­amino[3]ferrocenophane, the sequence of directed ortho-lithiation (t-BuLi), treatment with p-tosyl azide/sodium pyrophosphate (to yield the ortho-azido[3]ferrocenophane derivative) followed by catalytic hydrogenation gave the ortho-amino and α-dimethylamino[3]ferrocenophane derivatives. The potential use of some of the chelate ferrocenophane ligands in Ru-catalyzed asymmetric hydrogenations was investigated. Seven of the newly synthesized compounds were characterized by X-ray diffraction.

Key words

ferrocene - chelate ligand - amino group - P,N-ligand - asymmetric hydrogenation - catalysis

References

• 1a Josiphos: Togni A. Breutel C. Schnyder A. Spindler F. Landert H. Tijani A. J. Am. Chem. Soc.  1994,  116:  4062 
• 1b Ferrocenes - Homogeneous Catalysis, Organic Synthesis, Materials Science   Togni A. Hayashi T. Wiley-VCH; Weinheim: 1995. 
• 1c Metallocenes - Synthesis, Reactivity, Applications   Vol. 1:  Togni A. Halterman RL. Wiley-VCH; Weinheim: 1995. 
• 1d Metallocenes - Synthesis, Reactivity, Applications   Vol. 2:  Togni A. Halterman RL. Wiley-VCH; Weinheim: 1998. 
• 1e Colacot TJ. Chem. Rev.  2003,  103:  3101 
• 1f Dai L.-X. Tu T. You S.-L. Deng W.-P. Hou X.-L. Acc. Chem. Res.  2003,  36:  659 ; and references cited therein
• 2a Mernyi A. Kratky C. Weissensteiner W. Widhalm M. J. Organomet. Chem.  1996,  508:  209 
• 2b Gómez-de la Torre F. Jalón FA. López-Agenjo A. Manzano BR. Rodriguez A. Sturn T. Weissensteiner W. Martinez-Ripoll M. Organometallics  1998,  17:  4634 
• 2c Jalón FA. López-Aganjo A. Manzano BR. Moreno-Lara M. Rodriguez A. Sturm T. Weissensteiner W. J. Chem. Soc., Dalton Trans.  1999,  4031 
• 3 Liptau P. Seki T. Kehr G. Abele A. Fröhlich R. Erker G. Grimme S. Organometallics  2003,  22:  2226 
• Reviews:
• 4a Drent E. Budzelaar PHM. Chem. Rev.  1996,  96:  663 
• 4b Bianchini C. Meli A. Coord. Chem. Rev.  2002,  225:  35 
• 5a Gambs C. Chaloupka S. Consiglio G. Togni A. Angew. Chem. Int. Ed.  2000,  39:  2486 ; Angew. Chem. 2000, 112, 2602
• 5b Gambs C. Consiglio G. Togni A. Helv. Chim. Acta  2001,  84:  3105 
• 6 Liptau P. Tebben L. Kehr G. Fröhlich R. Erker G. Hollmann F. Rieger B. Eur. J. Org. Chem.  2005,  1909 
• 7a Knüppel S. Fröhlich R. Erker G. J. Organomet. Chem.  1999,  586:  218 
• 7b Knüppel S. Fröhlich R. Erker G. J. Organomet. Chem.  2000,  595:  308 
• See also:
• 8a Knüppel S. Erker G. Fröhlich R. Angew. Chem. Int. Ed.  1999,  38:  1923 ; Angew. Chem. 1999, 111, 2048
• 8b Bai S.-D. Wie X.-H. Guo J.-P. Liu D.-S. Zhou Z.-Y. Angew. Chem. Int. Ed.  1999,  38:  1927 ; Angew. Chem. 1999, 111, 2051
• 8c Knüppel S. Wang C. Kehr G. Fröhlich R. Erker G. J. Organomet. Chem.  2005,  690:  14 
• 9 Liptau P. Knüppel S. Kehr G. Kataeva O. Fröhlich R. Erker G. J. Organomet. Chem.  2001,  637-639:  621 
• 10a Liptau P. Tebben L. Kehr G. Wibbeling B. Fröhlich R. Erker G. Eur. J. Inorg. Chem.  2003,  3590; corrigendum p. -4261  
• 10b Tebben L. Kehr G. Fröhlich R. Erker G. Synthesis  2004,  1971 
• 11a Marquarding D. Klusacek H. Gokel GW. Hoffmann P. Ugi I. J. Am. Chem. Soc.  1970,  92:  5389 
• 11b Gokel GW. Marquarding D. Ugi I. J. Org. Chem.  1972,  37:  3052 
• 11c Hayashi T. Mise T. Fukushima M. Kagotani M. Nagashima N. Hamada Y. Matsumoto A. Kawakami S. Konishi M. Yamamoto K. Kumada M. Bull. Chem. Soc. Jpn.  1980,  53:  1138 
• 12a Tainturier G. y Sok Khay C. Gautheron B. C. R. Seances Acad. Sci., Ser. C  1973,  269:  1269 
• 12b y Sok Khay C. Tainturier G. Gautheron B. Tetrahedron Lett.  1974,  2207 
• 12c y Sok Khay C. Tainturier G. Gautheron B. J. Organomet. Chem.  1977,  132:  173 
• 12d Caynela EM. Xiao L. Sturm T. Manzano BR. Jalón FA. Weissensteiner W. Tetrahedron: Asymmetry  2000,  11:  861 
• 12e Manzano BR. Jalón FA. Gómez-de la Torre F. López-Agenjo AM. Rodríguez AM. Mereiter K. Weissensteiner W. Sturm T. Organometallics  2002,  21:  789 
• 12f Sturm T. Weissensteiner W. Spindler F. Mereiter K. López-Agenjo AM. Manzano BR. Jalón FA. Organometallics  2002,  21:  1766 ; and references therein
• 12g Liptau P. Neumann M. Erker G. Kehr G. Fröhlich R. Grimme S. Organometallics  2004,  23:  21 
• 13a Akabori S. Sato M. Ebine S. Synthesis  1981,  278 
• 13b Onishi M. Hiraki K. Iwamoto A. J. Organomet. Chem.  1984,  262:  C11 
• 13c Anderson JC. Blake AJ. Arnall-Culliford JC. Org. Biomol. Chem.  2003,  1:  3586 
• 14a Tebben L. Neumann M. Kehr G. Fröhlich R. Erker G. Losi S. Zanello P. Dalton Trans.  2006,  1715 
• 14b Tebben L. Neumann M. Kehr G. Fröhlich R. Erker G. Losi S. Zanello P. Chem. Sci.  2006,  3:  C29 
• 15a Wolfe JP. Wagaw S. Marcoux J.-F. Buchwald SL. Acc. Chem. Res.  1998,  31:  805 
• 15b Hartwig JF. Acc. Chem. Res.  1998,  31:  852 
• 15c Meyers C. Maes BUW. Loones KTJ. Bal G. Lemiere GLF. Dommisse RA. J. Org. Chem.  2004,  69:  6010 ; and references cited therein
• 16 Bertogg A. Camponovo F. Togni A. Eur. J. Inorg. Chem.  2005,  347 
• 17a Spagnolo P. Zanirato P. J. Org. Chem.  1978,  43:  3539 
• 17b Reed JN. Snieckus V. Tetrahedron Lett.  1983,  24:  3795 
• 17c Shafir A. Power MP. Whitener GD. Arnold J. Organometallics  2000,  19:  3978 
• 18 Oshima N. Suzuki H. Moro-Oka Y. Chem. Lett.  1984,  1161 
• 19 Ito M. Hirakawa M. Murata K. Ikariya T. Organometallics  2001,  20:  379 
• 20a Hashiguchi S. Fujii A. Takehara J. Ikariya T. Noyori R. J. Am. Chem. Soc.  1995,  117:  7562 
• 20b Gao J.-X. Ikariya T. Noyori R. Organometallics  1996,  15:  1087 
• 20c Noyori R. Hashiguchi S. Acc. Chem. Res.  1997,  30:  97 
• 20d Yamakawa M. Yamada I. Noyori R. Angew. Chem. Int. Ed.  2001,  40:  2818 ; Angew. Chem. 2001, 113, 2900
• 20e Watanabe M. Muratea K. Ikariya T. J. Org. Chem.  2002,  67:  1712 
• 20f Ohkuma T. Sandoval CA. Srinivasan R. Lin Q. Wei Y. Muniz K. Noyori R. J. Am. Chem. Soc.  2005,  127:  8288 
• 21 Gomez M. Jansat S. Muller G. Aullon G. Maestro MA. Eur. J. Inorg. Chem.  2005,  4341 
• 22 See for comparison: Liptau P. Carmona D. Oro LA. Lahoz FJ. Kehr G. Erker G. Eur. J. Inorg. Chem.  2004,  4586 
• 23a

  Nonius B.V., 1998

• 23b Otwinowski Z. Minor W. Methods Enzymol.  1997,  276:  307 
• 23c Blessing RH. Acta Crystallogr., Sect. A  1995,  51:  33 
• 23d Blessing RH. J. Appl. Crystallogr.  1997,  30:  421 
• 23e Otwinowski Z. Borek D. Majewski W. Minor W. Acta Crystallogr., Sect. A  2003,  59:  228 
• 23f Sheldrick GM. Acta Crystallogr., Sect. A  1990,  46:  467 
• 23g Structure refinement: Sheldrick GM. SHELXL-97   Universität Göttingen; Germany: 1997. 
• 23h Keller E. SCHAKAL   Universität Freiburg; Germany: 1997. 
• 23i

  CCDC 607475-607481 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre 12 Union Road Cambridge CB2 1EZ, UK; fax: [phone]].