Synlett 2012; 23(20): 2999-3000
DOI: 10.1055/s-0032-1317486
spotlight
© Georg Thieme Verlag Stuttgart · New York

Hendrickson Reagent (Triphenylphosphonium Anhydride Trifluoromethane Sulfonate)

Janice Irene McCauley
The School of Chemistry and Centre for Medicinal Chemistry, University of Wollongong, Wollongong NSW 2522 and The Shoalhaven Marine and Freshwater Centre, School of Biological Science, University of Wollongong, Shoalhaven Campus NSW 2541, Australia   Email: jim479@uowmail.edu.au
› Author Affiliations
Further Information

Publication History

Publication Date:
16 November 2012 (online)

Introduction

The Hendrickson reagent (triphenylphosphonium anhydride trifluoromethane sulfonate) was first reported in 1975.[ 1 ] It is readily prepared at 0 °C in dichloromethane from triphenylphosphine oxide and trifluromethanesulfonic anhydride in a 2:1 ratio and used directly as prepared in dichloromethane without the need for isolation.[1] [2] The Hendrickson reagent is a highly effective and versatile dehydrating reagent due to the strong electron-withdrawing capabilities of the triflyl group and special affinity for oxygen based on the very strong P–O bond.[ 3 ] It is selective for attack on oxygen without any intrinsic nucleophiles, avoiding formation of unwanted by-products. It has successfully been employed in ester, ether and amide formation as well as in the rapid conversion of aldoximes into nitriles, to yield a variety of alkyl and aryl aldoximes.[ 2–4 ] These reactions occur in a manner that is analogous to the Mitsunobu reaction, involving an intermediate alkoxyphosphonium salt.[5] [6] The advantages of the Hendrickson reagent over the Mitsunobu reagent are that the recovered triphenylphosphine oxide may be recycled by treatment with trifluromethanesulfonic anhydride, the use of explosive azodicarboxylates is not required and competing side reactions are avoided.[ 7 ] Furthermore, a number of methods have recently been reported that can easily overcome, or avoid, the formation and removal of the double-stoichiometric amount of triphenylphosphine oxide, a common problem of phosphine-based dehydrating agents. These methods employ novel derivatives of the Hendrickson reagent such as a copolymer-supported triphenylphosphine ditriflate, an insoluble support allowing for the easy removal of triphenylphosphine[ 8 ] or cyclic analogues that can eliminate the step of oxidizing the phosphine into the corresponding oxide prior to trifluoromethylsulfonation.[9] [10]

Zoom Image
Scheme 1 Preparation of the Hendrickson reagent
 
  • References

  • 1 Hendrickson JB, Schartzman SM. Tetrahedron Lett. 1975; 16: 277
  • 2 Hendrickson JB, Hussoin MdS. J. Org. Chem. 1987; 52: 4137
  • 3 Hendrickson JB, Hussoin MdS. Synlett 1990; 423
  • 4 Moussa Z, Ahmed SA, ElDouhaibi AS, Al-Raqa SY. Tetrahedron Lett. 2010; 51: 1826
  • 5 Mitsunobu O, Yamada M. Bull. Chem. Soc. Jpn. 1967; 40: 2380
  • 6 Mitsunobu O, Yamada M, Mukaiyama T. Bull. Chem. Soc. Jpn. 1967; 40: 935
  • 7 Elson KE, Jenkins ID, Loughin WA. Org. Biomol. Chem. 2003; 1: 2958
  • 8 Mahdavi H, Amani J. Tetrahedron Lett. 2008; 49: 2204
  • 9 Elson KE, Jenkins ID, Loughlin WA. Aus. J. Chem. 2004; 57: 371
  • 10 Moussa Z. Synthesis 2012; 44: 460
  • 11 Xi J, Dong Q.-L, Liu G.-S, Wang S, Chen L, Yao Z-J. Synlett 2010; 1674
  • 12 Xu M, Hou Q, Wang S, Wang H, Yao Z-J. Synthesis 2011; 1: 626
  • 13 Wu M, Wang S. Synthesis 2010; 587
  • 14 Xu P, Liu G-S, Xi J, Wang S, Yao Z-J. Tetrahedron 2011; 67: 5455
  • 15 Mossotti M, Panza L. J. Org. Chem. 2011; 76: 9122
  • 16 Zhou H.-B, Lui G.-S, Yao Z-J. Org. Lett. 2007; 9: 2003
  • 17 Fortunak JM. D, Mastrocola AR, Mellinger M, Sisti NJ, Wood JL, Zhuang Z-P. Tetrahedron Lett. 1996; 37: 5679