Organocatalytic Mitsunobu Reactions
with 3,5-Dinitrobenzoic Acid

Tracy Yuen Sze But; Jinni Lu; Patrick H. Toy

doi:10.1055/s-0029-1219795

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synlett 2010(7): 1115-1117
DOI: 10.1055/s-0029-1219795

LETTER

Organocatalytic Mitsunobu Reactions with 3,5-Dinitrobenzoic Acid

Tracy Yuen Sze But, Jinni Lu, Patrick H. Toy*
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. of China
Fax: +852 28571586; e-Mail: phtoy@hku.hk;

Further Information

Publication History

Received 4 February 2010
Publication Date:
23 March 2010 (online)

Abstract
Full Text
References
Supplementary Material

Permissions and Reprints All articles of this category

Abstract

A second generation procedure for organocatalytic Mitsunobu reactions using 3,5-dinitrobenzoic acid as the pro-nucleophile has been developed. The increased acidity of this acid compared to 4-nitrobenzoic acid, which was used in the original procedure, allowed for higher isolated yields of the desired products and eliminated formation of undesired acetate byproducts.

Key words

3,5-dinitrobenzoic acid - (diacetoxyiodo)benzene - catalytic oxidation - organocatalysis - Mitsunobu reaction

Supporting Information

References and Notes

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

Google Scholar
1b Mitsunobu O. Eguchi M. Bull. Chem. Soc. Jpn. 1971, 44: 3427

Google Scholar
1c Mitsunobu O. Kimura J. Fujisawa Y. Bull. Chem. Soc. Jpn. 1972, 46: 245

Google Scholar
1d Mitsunobu O. Wada M. Sano T. J. Am. Chem. Soc. 1972, 94: 679

Google Scholar
1e Wada M. Sano T. Mitsunobu O. Bull. Chem. Soc. Jpn. 1973, 46: 2833

Google Scholar
2 Mukaiyama T. Angew. Chem. Int. Ed. 1976, 15: 94

Google Scholar
For reviews on the Mitsunobu reaction, see:
3a Mitsunobu O. Synthesis 1981, 1

Google Scholar
3b Castro BR. Org. React. 1983, 29: 1

Google Scholar
3c Hughes DL. Org. React. 1992, 42: 335

Google Scholar
3d Hughes DL. Org. Prep. Proced. Int. 1996, 28: 127

Google Scholar
3e Dodge JA. Jones SA. Recent Res. Dev. Org. Chem. 1997, 1: 273

Google Scholar
3f Ren X.-F. Xu J.-L. Chen S.-H. Chin. J. Chem. 2006, 26: 454

Google Scholar
3g But TYS. Toy PH. Chem. Asian J. 2007, 2: 1340

Google Scholar
3h Golantsov NE. Karchava AV. Yurovskaya MA. Chem. Heterocycl. Compd. 2008, 44: 263

Google Scholar
3i Kumara Swamy KC. Bhuvan Kumar NN. Balaraman E. Pavan Kumar KVP. Chem. Rev. 2009, 109: 2551

Google Scholar
3j Reynolds AJ. Kassiou M. Curr. Org. Chem. 2009, 13: 1610

Google Scholar
4 For a review on the use of diazenes in organic synthesis, see: Košmrlj J. Kočevar M. Polanc S. Synlett 2009, 2217

Article in Thieme Connect Google Scholar
5 Constable DJC. Dunn PJ. Hayler JD. Humphrey GR. Leazer JL. Linderman RJ. Lorenz K. Manley J. Pearlman BA. Wells A. Zaks A. Zhang TY. Green Chem. 2007, 9: 411

Crossref Google Scholar
6a Dembinski R. Eur. J. Org. Chem. 2004, 2763

Google Scholar
6b Dandapani S. Curran DP. Chem. Eur. J. 2004, 10: 3130

Google Scholar
7 Choi MKW. He HS. Toy PH. J. Org. Chem. 2003, 68: 9831

Crossref PubMed Google Scholar
8 Harned AM. He HS. Toy PH. Flynn DL. Hanson PR. J. Am. Chem. Soc. 2005, 127: 52

Crossref Google Scholar
9 Arnold LD. Assil HI. Vederas JC. J. Am. Chem. Soc. 1989, 111: 3973

Crossref Google Scholar
10 Barrett AGM. Roberts RS. Schröder J. Org. Lett. 2000, 2: 2999

Crossref Google Scholar
11 Starkey GW. Parlow JJ. Flynn DL. Bioorg. Med. Chem. Lett. 1998, 8: 2385

Crossref Google Scholar
12a Dandapani S. Curran DP. Tetrahedron 2002, 58: 3855

Google Scholar
12b Dobbs AP. McGregor-Johnson C. Tetrahedron Lett. 2002, 43: 2807

Google Scholar
12c Dandapani S. Curran DP. J. Org. Chem. 2004, 69: 8751

Google Scholar
12d Chu Q. Henry C. Curran DP. Org. Lett. 2008, 10: 2453

Google Scholar
13 Dandapani S. Newsome JJ. Curran DP. Tetrahedron Lett. 2004, 45: 6653

Crossref Google Scholar
14 Poupon J.-C. Boezio AA. Charette AB. Angew. Chem. Int. Ed. 2006, 45: 1415

Crossref Google Scholar
15a Lipshutz BH. Chung DW. Rich B. Corral R. Org. Lett. 2006, 8: 5069

Google Scholar
15b Taft BR. Swift EC. Lipshutz BH. Synthesis 2009, 332

Google Scholar
16a Sugimura T. Hagiya K. Chem. Lett. 2007, 36: 566

Google Scholar
16b Hagiya K. Muramoto N. Misaki T. Sugimura T. Tetrahedron 2009, 65: 6109

Google Scholar
17 Iranpoor N. Firouzabadi H. Khalili D. Motevalli S. J. Org. Chem. 2008, 73: 4882

Crossref Google Scholar
18 But TYS. Toy PH. J. Am. Chem. Soc. 2006, 128: 9636

Crossref PubMed Google Scholar
19a Mitsunobu O. Kimura J. Fujisawa Y. Bull. Chem. Soc. Jpn. 1972, 45: 245

Google Scholar
19b Jarosz S. Glodek J. Za moljski A. Carbohydr. Res. 1987, 163: 289

Google Scholar
19c Martin SF. Dodge JA. Tetrahedron Lett. 1991, 32: 3017

Google Scholar
19d Dodge JA. Nissen JS. Presnell M. Org. Synth. 1996, 73: 110

Google Scholar
20a Mori K. Otsuka T. Oda M. Tetrahedron 1984, 40: 2929

Google Scholar
20b Mori K. Ikunaka M. Tetrahedron 1984, 40: 3471

Google Scholar
22 Shang Y. But TYS. Togo H. Toy PH. Synlett 2007, 67

Article in Thieme Connect Google Scholar

21

General Procedure for Catalytic Mitsunobu Reactions: To a solution of 10 (1.98 mmol) and the alcohol substrate (1.8 mmol) in anhydrous THF (11 mL) under a N₂ atmosphere, was added 2 (0.028 mL, 0.18 mmol) and 8 (1.16 g, 3.6 mmol). This was followed by the addition of a solution of 1 (0.94 g, 3.6 mmol) in anhydrous THF (4 mL) slowly by syringe pump (0.25 equiv/h). The reaction mixture was stirred for a total of 16 h and then was diluted with Et₂O (30 mL). The organic phase was separated and then washed sequentially with sat. aq NaHCO₃ (2 × 20 mL), and brine (20 mL), dried with Na₂SO₄, filtered and concentrated in vacuo. The crude product was purified by column chromatography. All ester products were characterized by ^¹H and ^¹³C NMR spectroscopy. Enantiomeric excesses were determined by HPLC. See Supporting Information for details

Supplementary Material

Supporting Information