Reactivity of phospha-Wittig reagents towards NHCs and NHOs.

作者: Malte Fischer , Jan-Erik Siewert , Christian Hering-Junghans , Priyanka Gupta , Wolgang Baumann

DOI: 10.1039/D1DT00071C

关键词: Wittig reactionReactivity (chemistry)Medicinal chemistryReagentChemistry

摘要: Phospha-Wittig reagents, RPPMe3 (R = Mes* 2,4,6-tBu3-C6H2; MesTer 2,6-(2,4,6-Me3C6H2)-C6H3; DipTer 2,6-(2,6-iPr2C6H3)-C6H3), can be considered as phosphine-stabilized phosphinidenes. In this study we show that PMe3 displaced by NHCs or NHOs. Interestingly, phosphinidene-like reactivity results in a subsequent C(sp2)-H activation of the exocyclic CH2 group This concept was further extended to allyl-apended NHOs, which resulted phosphine-substituted allyl species.

参考文章(50)
Kate Powers, Christian Hering-Junghans, Robert McDonald, Michael J. Ferguson, Eric Rivard, Improved synthesis of N-heterocyclic olefins and evaluation of their donor strengths Polyhedron. ,vol. 108, pp. 8- 14 ,(2016) , 10.1016/J.POLY.2015.07.070
Xufang Chen, Rhett C. Smith, John D. Protasiewicz, Cycloaddition of phosphanylidene-σ4-phosphoranes ArPPMe3and quinones to yield 1,3,2-dioxophospholanes Chem. Commun.. pp. 146- 147 ,(2004) , 10.1039/B309165A
Shashin Shah, Glenn P.A. Yap, John D. Protasiewicz, Crystal structure of the phosphanylidene-σ4-phosphorane DmpPPMe3 (Dmp=2,6-Mes2C6H3) and reactions with electrophiles Journal of Organometallic Chemistry. ,vol. 608, pp. 12- 20 ,(2000) , 10.1016/S0022-328X(00)00284-9
Xinhua Li, Deqing Lei, Michael Y. Chiang, Peter P. Gaspar, General approaches to phosphinidenes via retroadditions Journal of the American Chemical Society. ,vol. 114, pp. 8526- 8531 ,(1992) , 10.1021/JA00048A026
Yasuhiro Masaki, Shozo Yanagida, Chyongjin Pac, Evidence for the Formation of Emissive A–D–D′ Triplexes in Quenching of 1,4-Dicyanonaphthalene-Arene Exciplexes by Olefins Chemistry Letters. ,vol. 17, pp. 1305- 1308 ,(1988) , 10.1246/CL.1988.1305
Angela Marinetti, François Mathey, A Novel Entry to the PC‐Double Bond: the “Phospha‐Wittig” Reaction Angewandte Chemie. ,vol. 27, pp. 1382- 1384 ,(1988) , 10.1002/ANIE.198813821
Eugenijus Urnėžius, Shashin Shah, John D. Protasiewicz, Diphosphene and Phosphoranylidenephosphine Formation from a Terminal Phosphinidene Complex Phosphorus Sulfur and Silicon and The Related Elements. ,vol. 144, pp. 137- 139 ,(1999) , 10.1080/10426509908546201
Rhett C. Smith, Shashin Shah, Eugenijus Urnezius, John D. Protasiewicz, An unusual equilibrium chlorine atom transfer process and its potential for assessment of steric pressure by bulky aryls. Journal of the American Chemical Society. ,vol. 125, pp. 40- 41 ,(2003) , 10.1021/JA028422R
Shashin Shah, M. Cather Simpson, Rhett C. Smith, John D. Protasiewicz, Three Different Fates for Phosphinidenes Generated by Photocleavage of Phospha-Wittig Reagents ArPPMe3 Journal of the American Chemical Society. ,vol. 123, pp. 6925- 6926 ,(2001) , 10.1021/JA015767L