Efficient Multigram Syntheses of Air-Stable, Chiral Primary Phosphine Ligand Precursors via Palladium-Catalyzed Phosphonylation of Aryltriflates

Abstract

Air-stable, chiral primary phosphines have been synthesized on a multigram scale. The key synthetic step is an optimized palladium-catalyzed phosphonylation reaction of aryltriflates, which opens up a valuable synthetic route to a chiral scaffold that is easily derivatized into novel phosphines.

Key words

phosphorus - palladium - cross-coupling - asymmetric catalysis - air-stability

• References

• 1a Maier L In Organic Phosphorus Compounds . Vol. 1. Kosolapoff GM, Maier L. Wiley-Interscience; New York: 1972: 4
• 1b Higham LJ In Phosphorus Compounds: Advanced Tools in Catalysis and Material Sciences. In Catalysis by Metal Complexes. Vol. 37. Peruzzini M, Gonsalvi L. Springer; Germany: 2011: 1
• 2a Brynda M. Coord. Chem. Rev. 2005; 249: 2013
• 2b Katti KV, Pillarsetty N, Raghuraman K. Top. Curr. Chem. 2003; 229: 121
• 3a Yoshifuji M, Shibayama K, Inamoto N, Matsushita T, Nishimoto K. J. Am. Chem. Soc. 1983; 105: 2495
• 3b Yoshifuji M, Shibayama K, Toyota K, Inamoto N. Tetrahedron Lett. 1983; 24: 4227
• 4a Henderson W, Alley SR. J. Organomet. Chem. 2002; 656: 120
• 4b Pillarsetty N, Raghuraman K, Barnes CL, Katti KV. J. Am. Chem. Soc. 2005; 127: 331
• 5 Hiney RM, Higham LJ, Müller-Bunz H, Gilheany DG. Angew. Chem. Int. Ed. 2006; 45: 7248 ; Note the presence of peroxides will oxidize the phosphines and thus the presence of these should be avoided (aged ether solvents, sunlight, etc.)
• 6 Stewart B, Harriman A, Higham LJ. Organometallics 2011; 30: 5338
• 7 (R)-MOP currently retails at £116.00 for 100 mg at www.sigmaaldrich.com (07/07/2012).
• 8 Hayashi T. Acc. Chem. Res. 2000; 33: 354
• 9a Ficks A, Martinez-Botella I, Stewart B, Harrington RW, Clegg W, Higham LJ. Chem. Commun. 2011; 47: 8274
• 9b Ficks A, Hiney RM, Harrington RW, Gilheany DG, Higham LJ. Dalton Trans. 2012; 3515
• 10 Higham LJ, Clarke EF, Müller-Bunz H, Gilheany DG. J. Organomet. Chem. 2005; 690: 211

For comprehensive reviews, see:
• 11a Tappe FM. J, Trepohl VT, Oestreich M. Synthesis 2010; 3037
• 11b Beletskaya IP, Kazankova MA. Russ. J. Org. Chem. 2002; 38: 1391
• 11c Van der Jeught S, Stevens CV. Chem. Rev. 2009; 109: 2672
• 12a Kalek M, Stawinski J. Organometallics 2007; 26: 5840
• 12b Kalek M, Stawinski J. Organometallics 2008; 27: 5876
• 12c Kohler MC, Grimes TV, Wang X, Cundari TR, Stockland RA. Jr. Organometallics 2009; 28: 1193
• 13a Kurz L, Lee G, Morgans DJr, Waldyke MJ, Ward T. Tetrahedron Lett. 1990; 31: 6321
• 13b Petrakis KS, Nagabhushan TL. J. Am. Chem. Soc. 1987; 109: 2831
• 14 Lavén G, Stawinski J. Synlett 2009; 225
• 15 Kalek M, Ziadi A, Stawinski J. Org. Lett. 2008; 10: 4637
• 16 Mésangeau C, Yous S, Pérès B, Lesieur D, Besson T. Tetrahedron Lett. 2005; 46: 2465
• 17 Saha B, RajanBabu TV. J. Org. Chem. 2007; 72: 2357
• 18 Uozumi Y, Tanahashi A, Lee S.-Y, Hayashi T. J. Org. Chem. 1993; 58: 1945
• 19 Hosoya N, Hatayama A, Irie R, Sasaki H, Katsuki T. Tetrahedron 1994; 50: 4311 ; and references therein
• 20 Uozumi Y, Suzuki N, Ogiwara A, Hayashi T. Tetrahedron 1994; 50: 4293
• 21 Armanino N, Koller R, Togni A. Organometallics 2010; 29: 1771
• 22a SMART, SAINT and SADABS . Bruker AXS Inc; Madison (USA): 2004
• 22b CrysAlisPro. Agilent Technologies Ltd; Oxford (UK): 2008
• 22c COLLECT and EvalCCD . Nonius BV; Delft (The Netherlands): 2002
• 23 Sheldrick GM. Acta Crystallogr., Sect. A: Found. Crystallogr. 2008; 64: 112
• 24 Flack HD. Acta Crystallogr., Sect. A: Found. Crystallogr. 1983; 39: 876