Application of the Z-Selective Still–Gennari Olefination Protocol for the Synthesis of Z-α,β-Unsaturated Phosphonates

Abstract

Application of the Z-selective Still–Gennari modification of Horner–Wadsworth–Emmons (HWE) reaction for the olefination of acylphosphonates is presented. A series of new Z-α,β-unsaturated phosphonates containing a carbonyl or ester moiety in the β-position were obtained in up to 94% yield and with up to 96% Z-selectivity. The standard HWE olefination of the acylphosphonates, which was performed for comparison, was either unsuccessful at all, or resulted in an inferior Z-selectivity and lower isolated yields.

Key words

Still–Gennari olefination - Z-selective Horner–Wadsworth–Emmons reaction - α,β-unsaturated phosphonates - vinylphosphonates

• References

• 1a Kiełbasiński P. Góralczyk P. Mikołajczyk M. Wieczorek MW. Majzner R. Tetrahedron: Asymmetry 1998; 9: 2641
• 1b Kiełbasiński P. Rachwalski M. Mikołajczyk M. Szyrej M. Wieczorek MW. Wijtmans R. Rutjes FP. J. T. Adv. Synth. Catal. 2007; 349: 1387
• 1c Rachwalski M. Kwiatkowska M. Drabowicz J. Kłos M. Wieczorek MW. Szyrej M. Sieroń L. Kiełbasiński P. Tetrahedron: Asymmetry 2008; 19: 2096
• 1d Kaczmarczyk S. Kwiatkowska M. Madalińska L. Barbachowska A. Rachwalski M. Błaszczyk J. Sieroń L. Kiełbasiński P. Adv. Synth. Catal. 2011; 353: 2446
• 1e Kwiatkowska M. Janicki I. Kiełbasiński P. J. Mol. Catal. B: Enzym. 2015; 118: 23
• 1f Kiełbasiński P. Kwiatkowska M. Mikołajczyk M. In Future Directions in Biocatalysis . 2nd ed.; Matsuda T. Elsevier; Oxford: 2017: 191
• 2 Janicki I. Kiełbasiński P. Turrini NG. Faber K. Hall M. Adv. Synth. Catal. 2017; 359: 4190
• 3 Stueckler C. Hall M. Ehammer H. Pointner E. Kroutil W. Macheroux P. Faber K. Org. Lett. 2007; 9: 5409
• 4 Öhler E. El-Badawi M. Zbiral E. Monatsh. Chem. 1985; 116: 77
• 5 Harris RL. N. McFadden HG. Aust. J. Chem. 1984; 37: 417
• 6 Still WC. Gennari C. Tetrahedron Lett. 1983; 24: 4405
• 7a Kobayashi K. Tanaka KIII. Kogen H. Tetrahedron Lett. 2018; 59: 568
• 7b Bisceglia J. Á. Orelli LR. Curr. Org. Chem. 2012; 16: 2206
• 7c Bisceglia J. Á. Orelli LR. Curr. Org. Chem. 2015; 19: 744
• 7d Horner L. Hoffmann HM. R. Wippel HG. Chem. Ber. 1958; 91: 61
• 7e Horner L. Hoffmann HM. R. Wippel HG. Klahre G. Chem. Ber. 1959; 92: 2499
• 7f Wadsworth WS. Emmons WD. J. Am. Chem. Soc. 1961; 83: 1733
• 8a Yadav JS. Dhara S. Hossain SkS. Mohapatra DK. J. Org. Chem. 2012; 77: 9628
• 8b Yadav JS. Rao GM. Thirupathaiah B. Helv. Chim. Acta 2013; 96: 2233
• 8c Allais F. Aouhansou M. Majira A. Ducort PH. Synthesis 2010; 2787
• 8d Jala R. Nomula R. Krishna PR. Synth. Commun. 2017; 47: 1879
• 8e Reymond S. Cossy J. Tetrahedron 2007; 63: 5918
• 8f Thompson CM. Quinn CA. Hergenrother PJ. J. Med. Chem. 2009; 52: 117
• 9a Rübsam F. Evers AM. Michel C. Giannis A. Tetrahedron 1997; 53: 1707
• 9b Yu W. Su M. Jin Z. Tetrahedron Lett. 1999; 40: 6725
• 9c Franci X. Martina SL. X. McGrady JE. Webb MR. Donald C. Taylor RJ. K. Tetrahedron Lett. 2003; 44: 7735
• 9d Molnár K. Takács L. Kádár M. Faigl F. Kardos Z. Synth. Commun. 2017; 47: 1214
• 9e Maity S. Kanikarapu S. Marumudi K. Kunwar AC. Yadav JS. Mohapatra DK. J. Org. Chem. 2017; 82: 4561
• 10a Minami T. Motoyoshiya J. Synthesis 1992; 333
• 10b Adler P. Fadel A. Rabasso N. Tetrahedron 2014; 70: 4437
• 10c Dembitsky VM. Al Aziz Al Quntar A. Haj-Yehia A. Srebnik M. Mini-Rev. Org. Chem. 2005; 2: 91
• 11a Molnár K. Takács L. Kádár M. Kardos Z. Faigl F. Synthesis 2015; 47: 1085
• 11b Messik F. Oberthür M. Synthesis 2013; 45: 167