Enantioselective α-Hydroxylation of β-Keto Esters Catalyzed by Cinchona 
Alkaloid Derivatives

Yakun Wang; Zhi Li; Ting Xiong; Jingnan Zhao; Qingwei Meng

doi:10.1055/s-0034-1378548

Synlett, Inhaltsverzeichnis

Synlett 2014; 25(15): 2155-2160
DOI: 10.1055/s-0034-1378548

letter

Enantioselective α-Hydroxylation of β-Keto Esters Catalyzed by Cinchona Alkaloid Derivatives

Autor*innen

Yakun Wang

State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian 116024, P. R. of China Fax: +86(411)84986201 eMail: mengqw@dlut.edu.cn
Zhi Li

State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian 116024, P. R. of China Fax: +86(411)84986201 eMail: mengqw@dlut.edu.cn
Ting Xiong

State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian 116024, P. R. of China Fax: +86(411)84986201 eMail: mengqw@dlut.edu.cn
Jingnan Zhao

State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian 116024, P. R. of China Fax: +86(411)84986201 eMail: mengqw@dlut.edu.cn
Qingwei Meng*

State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian 116024, P. R. of China Fax: +86(411)84986201 eMail: mengqw@dlut.edu.cn

Abstract

Alle Artikel dieser Rubrik

Abstract

A highly efficient α-hydroxylation of β-keto esters catalyzed by cupreidine in the presence of cumyl hydroperoxide (CHP) was achieved. The reaction was applied to a wide variety of β-keto esters to give products in high yields (up to 95%) with excellent enantioselectivities (up to 97% ee). The reaction had been successfully scaled up to a gram quantity and (S)-5-chloro-2-hydroxy-1-oxo-2,3-dihydro-1H-indene-2-carboxylate – the important intermediate of Indoxacarb were obtained in 96% yield with 86% ee. The enantiomeric excess could be improved to 99% by crystallization, and this method has prospect of industrial application for its advantages of enantioselectivity, ease of catalyst preparation and reclamation of catalyst.

Key words

cinchona alkaloid - organocatalysis - enantioselectivity - β-keto esters - industrial application

Volltext

Referenzen

References and Notes
1 Christoffers J, Baro A, Werner T. Adv. Synth. Catal. 2004; 346: 143

2a Zhu J, Klunder AJ. H, Zwanenburg B. Tetrahedron Lett. 1994; 35: 2787
2b Christoffers J, Werner T, Frey W, Baro A. Chem. Eur. J. 2004; 10: 1042

3 Wellington KD, Cambie RC, Rutledge PS, Bergquist PR. J. Nat. Prod. 2000; 63: 79
4 Olack G, Morrison H. J. Org. Chem. 1991; 56: 4969
5 Davis FA, Clark C, Kumar A, Chen BC. J. Org. Chem. 1994; 59: 1184
6 Buchi G, Matsumoto KE, Nishimura H. J. Am. Chem. Soc. 1971; 93: 3299
7 Chooi Y, Hong YJ, Cacho RA, Tantillo DJ, Tang Y. J. Am. Chem. Soc. 2013; 135: 16805
8 Matsuda Y, Awakawa T, Wakimoto T, Abe I. J. Am. Chem. Soc. 2013; 135: 10962
9 McCann SF, Annis GD, Shapiro R, Piotrowski DW, Lahm GP, Long JK, Lee KC, Hughes MM, Myers BJ, Griswold SM, Reeves BM, March RW, Sharpe PL, Lowder P, Barnette WE, Wing KD. Pest Manag. Sci. 2001; 57: 153
10 Casalnuovo AL. WO 03002255, 2003
11 Toullec PY, Bonaccorsi C, Mezzetti A, Togni A. Proc. Natl. Acad. Sci. U.S.A. 2004; 101: 5810
12 Ishimaru T, Shibata N, Nagai J, Nakamura S, Toru T, Kanemasa S. J. Am. Chem. Soc. 2006; 128: 16488

13a Smith AM. R, Billen D, Hii KK. Chem. Commun. 2009; 3925
13b Smith AM, Rzepa HS, White AJ, Billen D, Hii KK. J. Org. Chem. 2010; 75: 3085

14 Li J, Cheng G, Wang Z, Zhang RZ, Zhang XM, Ding KL. Chem. Sci. 2011; 2: 1141
15 Jiang JJ, Wang D, Zhao MX, Shi M. Tetrahedron: Asymmetry 2010; 21: 794
16 Yin CK, Cao WD, Lin LL, Liu XH, Feng XM. Adv. Synth. Catal. 2013; 355: 1924
17 MacMillan DW. C. Nature (London, U.K.) 2008; 455: 304
18 Lu M, Zhu D, Lu YP, Zeng XF, Tan B, Xu ZJ, Zhong GF. J. Am. Chem. Soc. 2009; 131: 4562

19a Gong B, Meng QW, Su T, Lian MM, Wang Q, Gao ZX. Synlett 2009; 2659
19b Cai YC, Lian MM, Li Z, Meng QW. Tetrahedron 2012; 38: 7973

20a Lian MM, Li Z, Meng QW, Gao ZX. Eur. J. Org. Chem. 2010; 34: 6525
20b Yao HJ, Lian MM, Li Z, Wang YK, Meng QW. J. Org. Chem. 2012; 77: 9601
20c Lian MM, Li Z, Cai YC, Meng QW, Gao ZX. Chem Asian J. 2012; 7: 2019

21a Zou L, Wang B, Mu H, Zhang H, Song Y, Qu J. Org. Lett. 2013; 15: 3106
21b Minami O, Kota F, Tatsuya W, Nagazawa K. Chem. Eur. J. 2013; 19: 16740

22 Taylor EG. WO 03040083, 2003
23 Acocella MR, Mancheno OG, Bella M, Jørgensen KA. J. Org. Chem. 2004; 69: 8165
24 Marcelli T, Maarseveen JH. V, Hiemstra H. Angew. Chem. Int. Ed. 2006; 45: 7496
25 Li H, Wang Y, Tang L, Deng L. J. Am. Chem. Soc. 2004; 126: 9906

26a Xiao X, Xi Y, Su C, Liu M, Shi Y. J. Am. Chem. Soc. 2011; 133: 12914
26b Wu FH, Li HM, Hong R, Deng L. Angew. Chem. Int. Ed. 2006; 45: 947
26c He P, Liu X, Shi J, Lin L, Feng X. Org. Lett. 2011; 13: 936
26d Wu F, Hong R, Khan J, Liu X, Deng L. Angew. Chem. Int. Ed. 2006; 45: 4301
26e Wang Y, Liu X, Deng L. J. Am. Chem. Soc. 2006; 128: 3928
26f Rigby CL, Dixon DJ. Chem. Commun. 2008; 32: 3798

27 Typical Experimental Procedure (Table 3, Entry 2) β-Keto ester 1b (28.0 mg, 0.125 mmol) and catalyst CPD (7.8 mg, 0.025 mmol, 20 mol%) were added to a test tube equipped with a stirring bar and dissolved in CHCl₃ (1 mL). Cumyl hydroperoxide (0.250 mmol in CHCl₃ solution (2 equiv, 1 mL) was added. The mixture was stirred at –20 °C for 48 h. The reaction was monitored by TLC, and the solvent was removed under reduced pressure at the completion of the reaction. The residue was extracted with EtOAc (2 × 50 mL). The combined organic layers were washed with brine (20 mL), dried over anhydrous Na₂SO₄, filtered, and concentrated in vacuo. The residue was purified by flash chromatography (elution gradient: PE–EtOAc, 13:1–5:1) to afford 3b as white solid (28.5 mg, 95% yield, 83% ee); [α]_D ²⁰ +85.73 (c 0.1, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 7.74 (d, J = 8.2 Hz, 1 H), 7.50 (s, 1 H), 7.42 (d, J = 8.2 Hz, 1 H), 4.02 (s, 1 H), 3.75 (s, 3 H), 3.70 (d, J = 17.5 Hz, 1 H), 3.24 (d, J = 17.5 Hz, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 199.40, 171.54, 153.54, 142.89, 131.99, 129.09, 126.77, 126.40, 80.43, 53.63, 38.95. HRMS (ES⁺): m/z calcd for C₁₁H₉ClO₄ + H⁺: 241.0233; found: 241.0215. HPLC conditions (Chiralcel OD-H, hexane–i-PrOH, 90:10): 1 mL/min, 254 nm, t _R (major) = 14.8 min, t _R (minor) = 19.2 min.

Zusatzmaterial

Supporting Information (PDF) (opens in new window)