Carbohydrate-Derived Bis(oxazoline) Ligand in the Total Synthesis of Grenadamide

Abstract

Using an optimised carbohydrate-based bis(oxazoline) ligand and copper(I) triflate, unactivated aliphatic alkenes were cyclopropanated­ with simple ethyl diazoacetate, giving the corresponding products in good yields and high stereoselectivities. The trans-disubstituted cyclopropyl carboxylic acid ester derived from 1-nonene was subsequently used as the key intermediate for the synthesis of the (+)-enantiomer of the natural product (-)-grenadamide. The efficient and high-yielding approach towards grenadamide reported here is the first to utilise asymmetric cyclopropanation for the construction of the chiral cyclopropyl unit.

Key words

carbohydrates - ligand design - asymmetric catalysis - natural products - cyclopropanation

References

• 1a Liu H.-W. Walsh CT. In The Chemistry of the Cyclopropyl Group   Rappoport Z. John Wiley & Sons Ltd.; New York: 1987.  p.956 
• 1b Donaldson WA. Tetrahedron  2001,  57:  8589 
• 1c Taylor RE. Engelhardt FC. Schmitt MJ. Tetrahedron  2003,  59:  5623 
• 1d Wessjohann LA. Brandt W. Thiemann T. Chem. Rev.  2003,  103:  1625 
• 2a Burja AM. Banaigs B. Abou-Mansour E. Burgess JG. Wright PC. Tetrahedron  2001,  57:  9347 
• 2b Welker M. von Döhren H. FEMS Microbiol. Rev.  2006,  30:  530 
• 2c Tan LT. Phytochem.  2007,  68:  954 
• 3 Sitachitta N. Gerwick W. J. Nat. Prod.  1998,  61:  681 
• 4 Al Dulayymi JR. Baird MS. Jones K. Tetrahedron  2004,  60:  341 
• 5 Green R. Cheeseman M. Duffill S. Merritt A. Bull SD. Tetrahedron Lett.  2005,  46:  7931 
• 6 Avery TD. Culbert JA. Taylor DK. Org. Biomol. Chem.  2006,  4:  323 
• 7 Salim H. Piva O. Tetrahedron Lett.  2007,  48:  2059 
• For reviews on stereoselective cyclopropanation reactions, see:
• 8a Lebel H. Marcoux J.-F. Molinaro C. Charette AB. Chem. Rev.  2003,  103:  977 
• 8b Pellissier H. Tetrahedron  2008,  64:  7041 
• 9 Cullen WR. Sugi Y. Tetrahedron Lett.  1978,  19:  1635 
• 10 Jackson R. Thompson DJ. J. Organomet. Chem.  1978,  159:  C29 
• 11 Selke R. React. Kinet. Catal. Lett.  1979,  10:  135 
• 12 Sinou D. Descotes G. React. Kinet. Catal. Lett.  1980,  14:  463 
• For reviews, see:
• 13a Hale KJ. In Rodd’s Chemistry of Carbon Compounds   2nd ed., 2nd Suppl., Vol. 1E/F/G:  Sainsbury M. Elsevier; Amsterdam: 1993.  Chap. 23b. p.273 
• 13b Diéguez M. Pàmies O. Claver C. Chem. Rev.  2004,  104:  3189 
• 13c Diéguez M. Claver C. Pàmies O. Eur. J. Org. Chem.  2007,  4621 
• 13d Boysen MMK. Chem. Eur. J.  2007,  13:  8648 
• 13e Benessere V. Del Litto R. De Roma A. Ruffo F. Coord. Chem. Rev.  2010,  254:  390 
• 14a Desimoni G. Faita G. Jørgensen KA. Chem. Rev.  2006,  106:  3561 
• 14b McManus HA. Guiry PF. Chem. Rev.  2004,  104:  4151 
• 14c Ghosh AK. Mathivanan P. Capiello J. Tetrahedron: Asymmetry  1998,  9:  1 
• 15 Desimoni G. Faita G. Quadrelli P. Chem. Rev.  2003,  103:  119 
• 16a Irmak M. Groschner A. Boysen MMK. Chem. Commun.  2007,  177 
• 16b Irmak M. Boysen MMK. Adv. Synth. Catal.  2008,  350:  403 
• 16c Minuth T. Boysen MMK. Synlett  2008,  1483 
• 16d Minuth T. Irmak M. Groschner A. Lehnert T. Boysen MMK. Eur. J. Org. Chem.  2009,  997 
• 16e Minuth T. Boysen MMK. Beilstein J. Org. Chem.  2010,  6:  doi:10.3762/bjoc.6.23 
• 17a Evans DA. Woerpel KA. Hinman MM. Faul MM. J. Am. Chem. Soc.  1991,  113:  726 
• 17b Loewenthal RE. Abiko A. Masamune S. Tetrahedron Lett.  1990,  31:  6005 
• 18a With semicorrin ligands, see: Fritschi H. Leutenegger U. Pfaltz A. Helv. Chim. Acta  1988,  71:  1553 
• 18b With polymer-bound azabis(oxazolines), see: Werner H. Herrerías CI. Glos M. Gissibl A. Fraile JM. Pérez I. Mayoral JA. Reiser O. Adv. Synth. Catal.  2006,  348:  125 
• 19a With planar chiral ligands, see: Lo MM.-C. Fu GC. J. Am. Chem. Soc.  1998,  120:  10270 
• 19b With boron-bridged bis(oxazolines), see: Mazet C. Köhler V. Pfaltz A. Angew. Chem. Int. Ed.  2005,  44:  4888 
• 20a Omura K. Swern D. Tetrahedron  1978,  34:  1651 
• 20b Lou Y. Horikawa M. Kloster RA. Hawryluk NA. Corey EJ. J. Am. Chem. Soc.  2004,  126:  8916 
• 21 He R. Deng M.-Z. Tetrahedron  2002,  58:  7613 
• 22 Ley SV. Priour A. Eur. J. Org. Chem.  2002,  3995