Thieme Chemistry Journal Awardees - Where
Are They Now? Bifunctional Organocatalysis
with N-Formyl-l-Proline:
A Novel Approach to Epoxide Ring Opening and Sulfide Oxidation

Shengwei Wei; Kerstin A. Stingl; Katharina M. Weiß; Svetlana B. Tsogoeva

doi:10.1055/s-0029-1219363

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Synlett 2010(5): 707-711
DOI: 10.1055/s-0029-1219363

LETTER

Thieme Chemistry Journal Awardees - Where Are They Now? Bifunctional Organocatalysis with N-Formyl-l-Proline: A Novel Approach to Epoxide Ring Opening and Sulfide Oxidation

Shengwei Wei, Kerstin A. Stingl, Katharina M. Weiß, Svetlana B. Tsogoeva*
Department of Chemistry and Pharmacy, Chair of Organic Chemistry I, University of Erlangen-Nuremberg, Henkestr. 42, 91054 Erlangen, Germany
Fax: +49(9131)8526865; e-Mail: tsogoeva@chemie.uni-erlangen.de;

Further Information

Publication History

Received 9 October 2009
Publication Date:
08 February 2010 (online)

Abstract
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Abstract

A conceptually distinct approach to the aminolysis of 1,2-epoxides, which involves Lewis base-Brønsted acid catalysis employing N-formyl-l-proline as an easily accessible bifunctional organocatalyst and water as a solvent is presented. The potential of N-formyl-l-proline as organocatalyst for the sulfide oxidation reaction using aqueous hydrogen peroxide as environmentally benign and readily available oxidant is also demonstrated. Good to high yields are achieved for both reactions.

Key words

bifunctional organocatalysis - Lewis base-Brønsted acid - epoxides - ring opening - amino alcohols - sulfide oxidation - sulfoxides

References and Notes

1a Dalko PI. Moisan L. Angew. Chem. Int. Ed. 2004, 43: 5138 ; Angew. Chem. 2004, 116, 5248

Google Scholar
1b Tian SK. Chen Y. Hang J. Tang L. McDaid P. Deng L. Acc. Chem. Res. 2004, 37: 621

Google Scholar
1c Miller SJ. Acc. Chem. Res. 2004, 37: 601

Google Scholar
2a Jagtap SB. Tsogoeva SB. Chem. Commun. 2006, 4747

Google Scholar
2b Baudequin C. Chaturvedi D. Tsogoeva SB. Eur. J. Org. Chem. 2007, 2623

Google Scholar
2c
Stingl, K., Tsogoeva,
S. B. unpublished results.
3a Wu S. Takeya R. Eto M. Tomizawa C. J. Pestic. Sci. 1987, 12: 221

Google Scholar
3b Corey EJ. Bakshi RK. Shibata S. Chen CP. Singh VK. J. Am. Chem. Soc. 1987, 109: 7925

Google Scholar
3c Rogers GA. Parson SM. Anderson DC. Nilsson LM. Bhar BA. Kornreich WD. Kaufman R. Jacobs RS. Kirtman B. J. Med. Chem. 1989, 32: 1217

Google Scholar
3d Auvin-Guette C. Rebuffat S. Prigent Y. Bodo B.
J. Am. Chem. Soc. 1992, 114: 2170

Google Scholar
3e Takehara J. Hashiguchi S. Fujii A. Inoue SI. Ikaria T. Nayori R. Chem. Commun. 1996, 233

Google Scholar
3f Ager DJ. Prakash I. Schaad DR. Chem. Rev. 1996, 96: 835

Google Scholar
3g Bergmeier SC. Tetrahedron 2000, 56: 2561

Google Scholar
3h Lee H.-S. Kang SH. Synlett 2004, 1673

Google Scholar
4 For excellent review on metal-mediated ring-opening reactions of epoxides, see: Schneider C. Synthesis 2006, 3919

Article in Thieme Connect Google Scholar
For selected recent examples, see, for Sc(OTf)₃:
5a Schneider C. Sreekanth AR. Mai E. Angew. Chem. Int. Ed. 2004, 43: 5691 ; Angew. Chem. 2004, 116, 5809

Google Scholar
5b Placzek AT. Donelson JL. Trivedi R. Gibbs RA. De S K. Tetrahedron Lett. 2005, 46: 9029

Google Scholar
For LiClO₄:
5c Heydari A. Mehrdad M. Maleki A. Ahmadi N. Synthesis 2004, 1563

Google Scholar
5d Azizi N. Saidi MR. Can. J. Chem. 2005, 83: 505

Google Scholar
For LiBr:
5e Chakraborti AK. Rudrawar S. Kondaskar A. Eur. J. Org. Chem. 2004, 3597

Google Scholar
5f Babic A. Sova M. Gobec S. Pecar S. Tetrahedron Lett. 2006, 47: 1733

Google Scholar
For Al(OTf)₃:
5g Fringuelli F. Pizzo F. Tortoioli S. Vaccaro L. J. Org. Chem. 2004, 69: 7745

Google Scholar
5h Williams DBG. Lawton M. Tetrahedron Lett. 2006, 47: 6557

Google Scholar
For BiCl₃:
5i McCluskey A. Leitch SK. Garner J. Caden CE. Hill TA. Odell LR. Stewart SG. Tetrahedron Lett. 2005, 46: 8229

Google Scholar
For Bi(OTf)₃ and Bi(TFA)₃:
5j Khodaei MM. Khosropour AR. Ghozati K. Tetrahedron Lett. 2004, 45: 3525

Google Scholar
For CoCl₂:
5k Sundararajan G. Vijayakrishna K. Varghese B. Tetrahedron Lett. 2004, 45: 8253

Google Scholar
For Cu(BF₄)₂:
5l Kamal A. Ramu R. Azhar MA. Khanna GBR. Tetrahedron Lett. 2005, 46: 2675

Google Scholar
5m Yarapathy VR. Mekala S. Rao BV. Tammishetti S. Catal. Commun. 2006, 7: 466

Google Scholar
For K₅CoW₁₂O₄₀˙3H₂O and (NH₄)₈[CeW₁₀O₃₆]˙20H₂O:
5n Mirkhani V. Tangestaninejad S. Yadollahi B. Alipanah L. Catal. Lett. 2005, 101: 93

Google Scholar
5o Rafiee E. Tangestaninejad S. Habibi MH. Mirkhani V. Synth. Commun. 2004, 34: 3673

Google Scholar
For [Cr(salen)Cl]:
5p Bartoli G. Bosco M. Carlone A. Locatelli M. Massaccesi M. Melchiorre Sambri L. Org. Lett. 2004, 6: 2173

Google Scholar
5q Kureshy RI. Sing S. Khan N. Abdi SHR. Agrawal S. Jasra RV. Tetrahedron: Asymmetry 2006, 17: 1638

Google Scholar
6 Ranu BC. Jana U. J. Org. Chem. 1998, 63: 8212

Crossref Google Scholar
7a Fan R.-H. Hou X.-L. J. Org. Chem. 2003, 68: 726

Google Scholar
7b Wu J. Xia H.-G. Green Chem. 2005, 7: 708

Google Scholar
7c Surendra K. Krishnaveni NS. Rao KR. Synlett 2005, 506

Google Scholar
7d Kleiner CM. Schreiner PR. Chem. Commun. 2006, 4315

Google Scholar
7e Fleming EM. Quigley C. Rozas I. Connon SJ. J. Org. Chem. 2008, 73: 948

Google Scholar
7f Connon SJ. Synlett 2009, 354

Google Scholar
7g Rajesh Krishnan G. Sreekumar K. Polymer 2008, 49: 5233

Google Scholar
For examples of aminolysis of 1,2-epoxides in the absence of any catalyst, see:
7h Azizi M. Saidi MR. Org. Lett. 2005, 7: 3649

Google Scholar
7i Bonollo S. Fringuelli F. Pizzo F. Vaccaro L. Green Chem. 2006, 8: 960

Google Scholar
7j Desai H. D’Souza BR. Foether D. Johnson BF. Lindsay HA. Synthesis 2007, 902

Google Scholar
For excellent reviews on water as a solvent, see:
8a Li C.-J. Chen L. Chem. Soc. Rev. 2006, 35: 68

Google Scholar
8b Herrerías CI. Yao XQ. Li ZP. Li C.-J. Chem. Rev. 2007, 107: 2546

Google Scholar
8c Dallinger D. Kappe CO. Chem. Rev. 2007, 107: 2563

Google Scholar
8d Chanda A. Fokin VV. Chem. Rev. 2009, 109: 725

Google Scholar
8e Gruttadauria M. Giacalone F. Noto R. Adv. Synth. Catal. 2009, 351: 33

Google Scholar
8f Paradowska J. Stodulski M. Mlynarski J. Angew. Chem. Int. Ed. 2009, 48: 4288 ; Angew. Chem. 2009, 121, 4352

Google Scholar
8g
For ring opening in water, see also ref. 7a-d,h,i.

Google Scholar
9a Carreño MC. Chem. Rev. 1995, 95: 1717

Google Scholar
9b Fernández I. Khiar N. Chem. Rev. 2003, 103: 3651

Google Scholar
For selected examples, see:
10a Di Furia F. Modena G. Seraglia R. Synthesis 1984, 325

Google Scholar
10b Pitchen P. Duñach E. Desmukh MN. Kagan HB. J. Am. Chem. Soc. 1984, 106: 8188

Google Scholar
10c Palucki M. Hanson P. Jacobsen EN. Tetrahedron Lett. 1992, 33: 7111

Google Scholar
10d Komatsu N. Hashizume M. Sugita T. Uemura S. J. Org. Chem. 1993, 58: 4529

Google Scholar
10e Bolm C. Bienewald F. Angew. Chem., Int. Ed. Engl. 1995, 34: 2640 ; Angew. Chem. 1995, 107, 2883

Google Scholar
10f Kokubo C. Katsuki T. Tetrahedron 1996, 52: 13895

Google Scholar
10g Lattanzi A. Bonadies F. Senatore A. Soriente A. Scettri A. Tetrahedron: Asymmetry 1997, 8: 2473

Google Scholar
10h Gunaratne HQN. McKervey MA. Feutren S. Finlay J. Boyd J. Tetrahedron Lett. 1998, 39: 5655

Google Scholar
10i Legros J. Bolm C. Angew. Chem. Int. Ed. 2004, 43: 4225 ; Angew. Chem. 2004, 116, 4321

Google Scholar
10j Drago C. Caggiano L. Jackson RFW. Angew. Chem. Int. Ed. 2005, 44: 7221 ; Angew. Chem. 2005, 117, 7387

Google Scholar
10k Legros J. Bolm C. Chem. Eur. J. 2005, 11: 1086

Google Scholar
10l Mba M. Prins LJ. Licini G. Org. Lett. 2007, 9: 21

Google Scholar
10m Egami H. Katsuki T. J. Am. Chem. Soc. 2007, 129: 8940

Google Scholar
10n Zeng Q.-L. Tang H.-Y. Zhang S. Liu J.-C. Chin. J. Chem. 2008, 26: 1435

Google Scholar
10o Sahoo S. Kumar P. Lefebvre F. Halligudi SB. J. Catal. 2009, 262: 111

Google Scholar
For metal-free procedures of sulfoxidation, see:
11a Tohma H. Takizawa S. Watanabe H. Fukuoka Y. Maegawa T. Kita Y. J. Org. Chem. 1999, 64: 3519

Google Scholar
11b Bethell D. Page PCB. Vahedi H. J. Org. Chem. 2000, 65: 6756

Google Scholar
11c Imada Y. Iida H. Ono S. Murahashi S.-I. J. Am. Chem. Soc. 2003, 125: 2868

Google Scholar
11d Salgaonkar PD. Shukla VG. Akamanchi KG. Synth. Commun. 2005, 35: 2805

Google Scholar
11e Hong-Bing J. Xiao-Fang H. Dong-Po S. Zhong L. Russ. J. Org. Chem. 2006, 42: 959

Google Scholar
11f Baxová L. Cibulka R. Hampl F. J. Mol. Catal. A: Chem. 2007, 277: 53

Google Scholar
11g Shi F. Tse MK. Kaiser HM. Beller M. Adv. Synth. Catal. 2007, 349: 2425

Google Scholar
11h del Río RE. Wang B. Achab S. Bohé L. Org. Lett. 2007, 9: 2265

Google Scholar
11i Golchoubian H. Hosseinpoor F. Molecules 2007, 12: 304

Google Scholar
11j Xiong Z.-G. Zhang J. Hu X.-M. Appl. Catal., A 2008, 334: 44

Google Scholar
11k Russo A. Lattanzi A. Adv. Synth. Catal. 2009, 351: 521

Google Scholar
13a Overman LE. Flippin LA. Tetrahedron Lett. 1981, 22: 195

Google Scholar
13b Woodgate PD. Singh Y. Rickard CEF.
J. Organomet. Chem. 1998, 560: 197

Google Scholar
13c Periasamy M. Kumar NS. Sivakumar S. Rao VD. Ramanathan CR. Venkatraman L. J. Org. Chem. 2001, 66: 3828

Google Scholar
13d Carrée F. Gil R. Collin J. Org. Lett. 2005, 7: 1023

Google Scholar
13e Kureshy RI. Singh S. Khan NH. Abdi SHR. Agrawal S. Mayani VJ. Jasra RV. Tetrahedron Lett. 2006, 47: 5277

Google Scholar
13f Bonollo S. Fringuelli F. Pizzo F. Vaccaro L. Synlett 2008, 1574

Google Scholar
13g Kureshy RI. Prathap KJ. Agrawal S. Khan NH. Abdi SHR. Jasra RV. Eur. J. Org. Chem. 2008, 18: 3118

Google Scholar
13h Hosseini-Sarvari M. Can. J. Chem. 2008, 86: 65

Google Scholar

12

General Procedure for the Aminolysis of 1,2-Epoxides A mixture of epoxide (0.31 mmol, 1 equiv), amine (2 equiv), and N-formyl-l-proline (0.1 equiv) in H₂O (150 µL) was stirred at r.t. for 24 or 48 h. The reaction mixture was diluted with H₂O (1.5 mL) and extracted with CH₂Cl₂ (3 × 2 mL). The combined organic layers were washed with brine (2 mL), dried (Na₂SO₄), and the solvent was removed under reduced pressure. The residue was purified by chromatog-raphy (SiO₂, PE-EtOAc) to provide the desired β-amino alcohols in yields given in Table [²] . Products from the entries 1-5 and 7-13 are known compounds. Their constitution was ascertained by comparison of spectroscopic data with reported literature data.^{7h, ¹³} β-Amino alcohol from entry 6 is a new compound, and its characterization data are reported below.
^¹H NMR (300 MHz, DMSO-d ₆): δ = 7.26 (t, 1 H, J = 7.5 Hz), 6.29-6.35 (m, 2 H), 5.65 (br s., 1 H), 3.24-3.45 (m, 2 H), 2.23 (s, 3 H), 1.85-1.96 (m, 2 H), 1.60-1.63 (m, 2 H), 1.08-1.22 (m, 4 H) ppm. ^¹³C NMR (75 MHz, DMSO-d ₆):
δ = 158.33, 154.56, 137.41, 110.26, 105.50, 73.21, 56.18, 34.20, 30.97, 24.13, 23.71 ppm. MS (MALDI): m/z = 207 [M + H]⁺; the exact molecular mass m/z = 206.1419 ± 1.7 ppm [M⁺] was confirmed by HRMS (EI, 70 eV).

14

A Typical Procedure for the Oxidation of Methyl Phenyl Sulfide To a solution of catalyst (0.048 mmol) in a solvent (500 µL) methyl phenyl sulfide (0.242 mmol) was added at r.t. To this mixture 30% H₂O₂ (29.6 µL, 1.2 equiv) was added in one portion and stirred for 24 h at r.t. After quenching the reaction with Na₂SO₃, the conversion was determined by GC analysis using hexadecane 99% (30 µL) as internal standard. The yield of isolated product was obtained directly by column chromatography (PE-EtOAc, 1:1). The isolated methyl phenyl sulfoxide was identified through comparison of ^¹H NMR spectra with literature data. See ref. 10g,k,m.