Download PDF
Synthesis 2007(8): 1185-1196  
DOI: 10.1055/s-2007-965973
PAPER
© Georg Thieme Verlag Stuttgart · New York

Modular Design of Pyridine-Based Acyl-Transfer Catalysts

Ingmar Held, Shangjie Xu, Hendrik Zipse*
Department Chemie und Biochemie, LMU München, Butenandtstraße 5-13, 81377 München, Germany
Fax: +49(89)218077738; e-Mail: zipse@cup.uni-muenchen.de;
Further Information

Publication History

Received 24 January 2007
Publication Date:
28 February 2007 (online)

    Permissions and Reprints All articles of this category

Abstract

Derivatives of 3,4-diaminopyridine have been synthesized and studied as catalysts for acyl-transfer reactions. The design of these catalysts is guided by the stability of their acetyl intermediates as determined through theoretical calculations at the B3LYP/6-311 + G(d,p)//B3LYP/6-31G(d) level of theory. The most promising catalysts have been synthesized through a three- to five-step synthesis starting from 3,4-diaminopyridine. The catalytic activity has been determined for the acylation of 1-ethynylcyclohexanol with acetic anhydride at 23 °C and with isobutyric anhydride at 40 °C. For both reactions, the catalytic activity depends dramatically on the substitution pattern of the diaminopyridines. Best results are obtained with catalysts containing alkyl substituents at both amine nitrogens.

Key words

catalysis - nucleophilic pyridines - acylation - alcohols

    References

  • For reviews see:
  • 1a Höfle G. Steglich W. Vorbrüggen H. Angew. Chem., Int. Ed. Engl.  1978,  17:  569 ; Angew. Chem. 1978, 90, 602
    CrossrefGoogle Scholar
  • 1b Scriven EFV. Chem. Soc. Rev.  1983,  12:  129 
    CrossrefGoogle Scholar
  • 1c Hassner A. In Encyclopedia of Reagents for Organic Synthesis   Paquette L. Wiley; Chichester: 1995.  p.2022 
    CrossrefGoogle Scholar
  • 1d Ragnarsson U. Grehn L. Acc. Chem. Res.  1998,  31:  494 
    CrossrefGoogle Scholar
  • 1e Spivey AC. Maddaford A. Redgrave A. Org. Prep. Proced. Int.  2000,  32:  331 
    CrossrefGoogle Scholar
  • 1f Berry DJ. Digiovanna CV. Metrick SS. Murugan R. ARKIVOC  2001,  (i):  201 ; www.arkat-usa.org
    CrossrefGoogle Scholar
  • 1g Spivey AC. Arseniyadis S. Angew. Chem. Int. Ed.  2004,  43:  5436 ; Angew. Chem. 2004, 116, 5552
    CrossrefGoogle Scholar
  • 2a Vedejs E. Jure M. Angew. Chem. Int. Ed.  2005,  44:  3971 ; Angew. Chem. 2005, 117, 4040
    CrossrefGoogle Scholar
  • 2b Dalko PI. Moisan L. Angew. Chem. Int. Ed.  2004,  43:  5138 ; Angew. Chem. 2004, 116, 5248
    CrossrefGoogle Scholar
  • 2c Fu G. Acc. Chem. Res.  2004,  37:  542 
    CrossrefGoogle Scholar
  • 2d France S. Guerin DJ. Miller SJ. Lectka T. Chem. Rev.  2003,  103:  2985 
    CrossrefGoogle Scholar
  • 2e Spivey AC. Maddaford A. Redgrave A. Org. Prep. Proced. Int.  2000,  32:  331 
    CrossrefGoogle Scholar
  • 2f Fu G. Acc. Chem. Res.  2000,  33:  412 
    CrossrefGoogle Scholar
  • 3a Kawabata T. Stragies R. Fukaya T. Fuji K. Chirality  2003,  15:  71 
    CrossrefGoogle Scholar
  • 3b Kawabata T. Stragies R. Fukaya T. Nagaoka Y. Schedel H. Fuji K. Tetrahedron Lett.  2003,  44:  1545 
    CrossrefGoogle Scholar
  • 4a Priem G. Pelotier B. Macdonald SJF. Anson MS. Campbell IB. J. Org. Chem.  2003,  68:  3844 
    CrossrefGoogle Scholar
  • 4b Pelotier B. Priem G. Macdonald SJF. Anson MS. Upton RJ. Campbell IB. Tetrahedron Lett.  2005,  46:  9005 
    CrossrefGoogle Scholar
  • 5a Spivey AC. Fekner T. Spey SE. Adams H. J. Org. Chem.  1999,  64:  9430 ; and references cited therein
    CrossrefGoogle Scholar
  • 5b Spivey AC. Fekner T. Spey SE. J. Org. Chem.  2000,  65:  3154 
    CrossrefGoogle Scholar
  • 5c Spivey AC. Maddaford A. Fekner T. Redgrave AJ. Frampton CS. J. Chem. Soc., Perkin Trans. 1  2000,  3460 
    CrossrefGoogle Scholar
  • 5d Spivey AC. Maddaford A. Fekner T. Leese DP. Redgrave AJ. Frampton CS. J. Chem. Soc., Perkin Trans. 1  2001,  1785 
    CrossrefGoogle Scholar
  • 5e Malardier-Jugroot C. Spivey AC. Whitehead MA. J. Mol. Struct. (THEOCHEM)  2003,  623:  263 
    CrossrefGoogle Scholar
  • 5f Spivey AC. Leese DP. Zhu F. Davey SG. Jarvest RL. Tetrahedron  2004,  60:  4513 
    CrossrefGoogle Scholar
  • 5g Spivey AC. Arseniyadis S. Fekner T. Maddaford A. Lees DP. Tetrahedron  2006,  62:  295 
    CrossrefGoogle Scholar
  • 6a Dalaigh CO. Hynes SJ. Maher DJ. Connon SJ. Org. Biomol. Chem.  2005,  3:  981 
    CrossrefGoogle Scholar
  • 6b Dalaigh CO. Hynes SJ. O’Brien JE. McCabe T. Maher DJ. Watson GW. Connon SJ. Org. Biomol. Chem.  2006,  4:  2785 
    CrossrefGoogle Scholar
  • 7a Shaw SA. Aleman P. Vedejs E. J. Am. Chem. Soc.  2003,  125:  13368 
    CrossrefPubMedGoogle Scholar
  • 7b Shaw SA. Aleman P. Christy J. Kampf JW. Va P. Vedejs E. J. Am. Chem. Soc.  2006,  128:  925 
    CrossrefPubMedGoogle Scholar
  • 8 Yamada S. Misono T. Iwai Y. Tetrahedron Lett.  2005,  46:  2239 
    CrossrefGoogle Scholar
  • 9a Miller SJ. Acc. Chem. Res.  2004,  37:  601 ; and references cited therein
    CrossrefGoogle Scholar
  • 9b Fierman MB. O’Leary DJ. Steinmetz WE. Miller SJ. J. Am. Chem. Soc.  2004,  126:  6967 
    CrossrefGoogle Scholar
  • 9c Evans JW. Fierman MB. Miller SJ. Ellman JA. J. Am. Chem. Soc.  2004,  126:  8134 
    CrossrefGoogle Scholar
  • 9d Sculimbrene BR. Xu Y. Miller SJ. J. Am. Chem. Soc.  2004,  126:  13182 
    CrossrefGoogle Scholar
  • 9e Morgan AJ. Wang YK. Roberts MF. Miller SJ. J. Am. Chem. Soc.  2004,  126:  15370 
    CrossrefGoogle Scholar
  • 9f Lewis CA. Sculimbrene BR. Xu Y. Miller SJ. Org. Lett.  2005,  7:  3021 
    CrossrefGoogle Scholar
  • 9g Xu Y. Sculimbrene BR. Miller SJ. J. Org. Chem.  2006,  71:  4919 
    CrossrefGoogle Scholar
  • 10 Singh S. Das G. Singh OV. Han H. Org. Lett.  2007,  9:  401 
    CrossrefGoogle Scholar
  • 11 Heinrich MR. Klisa HS. Mayr H. Steglich W. Zipse H. Angew. Chem. Int. Ed.  2003,  42:  4826 ; Angew. Chem. 2003, 115, 4975
    CrossrefGoogle Scholar
  • 12 Held I. Villinger A. Zipse H. Synthesis  2005,  1425 
    Article in Thieme ConnectGoogle Scholar
  • 13 Mederski WWKR. Kux D. Knoth M. Schwarzkopf-Hofmann MJ. Heterocycles  2003,  4:  925 
    Google Scholar
  • 14 Armand J. Boulares L. Bellec C. Pinson J. Can. J. Chem.  1988,  66:  1500 
    CrossrefGoogle Scholar
  • 15 Moore ML. Org. React.  1949,  5:  301 
    Google Scholar
  • 16 Sotirou-Leventis C. Mao Z. Rawashdeh A.-MM. J. Org. Chem.  2000,  65:  6017 
    CrossrefGoogle Scholar
  • 17a Kison C. Meyer N. Opatz T. Angew. Chem. Int. Ed.  2005,  44:  5662 ; Angew. Chem. 2005, 117, 5807
    CrossrefGoogle Scholar
  • 17b

    The large dependence of the reaction yield on the age of the BH3·THF solution described in this publication could be verified for the reduction of 24.
    Crossref
  • 18 Sakamoto T. Miura N. Kondo Y. Yamanaka H. Chem. Pharm. Bull.  1986,  34:  2018 
    CrossrefGoogle Scholar
  • 19 Claridge TDW. High-Resolution NMR Techniques in Organic Chemistry, Tetrahedron Organic Chemistry Series   Vol. 19:  Pergamon; Oxford: 1999.  p.298 
    Google Scholar
  • 20 Xu S. Held I. Kempf B. Mayr H. Steglich W. Zipse H. Chem. Eur. J.  2005,  11:  4751 
    CrossrefGoogle Scholar
  • 21 Fischer CB. Xu S. Zipse H. Chem. Eur. J.  2006,  12:  5779 
    CrossrefGoogle Scholar
  • 24 Gottlieb HE. Kotyar V. Nudelman A. J. Org. Chem.  1997,  21:  7512 
    Google Scholar
  • 25 Frisch MJ. Trucks GW. Schlegel HB. Scuseria GE. Robb MA. Cheeseman JR. Montgomery JA. Vreven T. Kudin KN. Burant JC. Millam JM. Iyengar SS. Tomasi J. Barone V. Mennucci B. Cossi M. Scalmani G. Rega N. Petersson GA. Nakatsuji H. Hada M. Ehara M. Toyota K. Fukuda R. Hasegawa J. Ishida M. Nakajima T. Honda Y. Kitao O. Nakai H. Klene M. Li X. Knox JE. Hratchian HP. Cross JB. Bakken V. Adamo C. Jaramillo J. Gomperts R. Stratmann RE. Yazyev O. Austin AJ. Cammi R. Pomelli C. Ochterski JW. Ayala PY. Morokuma K. Voth GA. Salvador P. Dannenberg JJ. Zakrzewski VG. Dapprich S. Daniels AD. Strain MC. Farkas O. Malick DK. Rabuck AD. Raghavachari K. Foresman JB. Ortiz JV. Cui Q. Baboul AG. Clifford S. Cioslowski J. Stefanov BB. Liu G. Liashenko A. Piskorz P. Komaromi I. Martin RL. Fox DJ. Keith T. Al-Laham MA. Peng CY. Nanayakkara A. Challacombe M. Gill PMW. Johnson B. Chen W. Wong MW. Gonzalez C. Pople JA. Gaussian 03, Revision B.03   Gaussian, Inc.; Wallingford CT: 2004. 
    Google Scholar
22

The rate of reaction in these cases is hardly different from that of the uncatalyzed background reaction, making the exact determination of the half-lives rather difficult with the methodology employed here. The data given in Table [2] have been estimated from the conversion measured for reaction A up to 25 d, 17 h and 30 min and for reaction B up to 31 d, 17 h and 15 min. In both cases the reactions had not yet reached 50% conversion at these times.

23

The conversion of the reaction stopped at 59%. ESI-MS studies of the reaction mixture indicate that the catalyst does not survive the reaction conditions employed here.