Mitsunobu Reaction with 4-(Diphenylphosphino)benzoic Acid: A Separation-Friendly Bifunctional Reagent that Serves as Both a Reductant and a Pronucleophile

Natsuko Muramoto; Kazuki Yoshino; Tomonori Misaki; Takashi Sugimura

doi:10.1055/s-0032-1318327

Synthesis, Table of Contents

Synthesis 2013; 45(7): 931-935
DOI: 10.1055/s-0032-1318327

paper

Mitsunobu Reaction with 4-(Diphenylphosphino)benzoic Acid: A Separation-Friendly Bifunctional Reagent that Serves as Both a Reductant and a Pronucleophile

Natsuko Muramoto

Graduate School of Material Science, University of Hyogo, 3-2-1, Kohto, Kamigori, Hyogo 678-1297, Japan Fax: +81(791)580115 Email: sugimura@sci.u-hyogo.ac.jp

,

Kazuki Yoshino

Graduate School of Material Science, University of Hyogo, 3-2-1, Kohto, Kamigori, Hyogo 678-1297, Japan Fax: +81(791)580115 Email: sugimura@sci.u-hyogo.ac.jp

,

Tomonori Misaki

Graduate School of Material Science, University of Hyogo, 3-2-1, Kohto, Kamigori, Hyogo 678-1297, Japan Fax: +81(791)580115 Email: sugimura@sci.u-hyogo.ac.jp

,

Takashi Sugimura*

Graduate School of Material Science, University of Hyogo, 3-2-1, Kohto, Kamigori, Hyogo 678-1297, Japan Fax: +81(791)580115 Email: sugimura@sci.u-hyogo.ac.jp

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Abstract

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Abstract

4-(Diphenylphosphino)benzoic acid was used for the Mitsunobu reaction as a bifunctional reagent that served as both a reductant and a pronucleophile. When combined with di-2-methoxyethyl azodicarboxylate, inversion of a secondary alcohol stereospecifically occurred to give an ester carrying a phosphine oxide group. The reaction mixture was directly hydrolyzed to give an inverted secondary alcohol in sufficient stereo and chemical purities by the presently developed chromatography-free process in conjunction with basic extraction, drying, and concentration.

Key words

alcohols - substitution - Mitsunobu reaction - phosphorus

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References

References
1 Mitsunobu O, Yamada M. Bull. Chem. Soc. Jpn. 1967; 40: 2380

2a Mitsunobu O. Synthesis 1981; 1
2b Hughes DL. Org. React. 1992; 42: 335
2c Swamy KC. K, Kumar NN. B, Balaraman E, Kumar KV. P. P. Chem. Rev. 2009; 109: 2551

3a For reviews, see: Dembinski R. Eur. J. Org. Chem. 2004; 2763
3b Dandapani S, Curran DP. Chem. Eur. J. 2004; 10: 3130

4a But TY. S, Toy PH. J. Am. Chem. Soc. 2006; 128: 9636
4b Poupon JC, Boezio AA, Charette AB. Angew. Chem. Int. Ed. 2006; 45: 1415
4c Lipshutz BH, Chung DW, Rich B, Corral R. Org. Lett. 2006; 8: 5069
4d Taft BR, Swift EC, Lipshutz BH. Synthesis 2009; 332
4e Yang J, Dai L, Wang X, Chen Y. Tetrahedron 2011; 67: 1456

5 Sugimura T, Hagiya K. Chem. Lett. 2007; 36: 566
6 Hagiya K, Muramoto N, Misaki T, Sugimura T. Tetrahedron 2009; 65: 6109

7a O’Neil IA, Thompson S, Murray CL, Kalindjian SB. Tetrahedron Lett. 1998; 39: 7787
7b For combination of dppe and DMEAD, see: Hagiya K. Ph.D. Thesis . University of Hyogo; Japan: 2010

8 Compound 1 is commercially available and could be easily prepared without a noble metal catalyst, see: Ravindar V, Hemling H, Schumann H, Blum J. Synth. Commun. 1992; 22: 841
9 Phosphine oxide 5 is known to be removable by extraction, see: Yoakim C, Guse I, O’Meara JA, Thavonekham B. Synlett 2003; 473

10a Dodge JA, Trujillo JI, Presnell M. J. Org. Chem. 1994; 59: 234
10b Sammakia T, Jacobs JS. Tetrahedron Lett. 1999; 40: 2685
10c Sammakia T, Jacobs JS. Tetrahedron Lett. 1999; 40: 10921

11 Sugimura T. Eur. J. Org. Chem. 2004; 1185

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