Synthesis of Optically Active
2,5-Dialkylcyclohexane-1,4-diols and Their Application
in the Asymmetric Oxidation of Sulfides

Jiangtao Sun; Minghua Yang; Zhenya Dai; Chengjian Zhu; Hongwen Hu

doi:10.1055/s-2008-1067185

PAPER

Synthesis of Optically Active 2,5-Dialkylcyclohexane-1,4-diols and Their Application in the Asymmetric Oxidation of Sulfides

Jiangtao Sun*^a,b, Minghua Yang^a, Zhenya Dai^a, Chengjian Zhu*^a,c, Hongwen Hu^a
^a Department of Chemistry, Nanjing University, Nanjing 210093, P. R. of China
e-Mail: cjzhu@nju.edu.cn;
^b Department of Chemistry, Sundia MediTech (Shanghai) Co, Ltd., Shanghai 201203, P. R. of China
e-Mail: jtsun@sundia.com;
^c State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China
Fax: +86(21)51903505;

Abstract

All articles of this category

Abstract

A simple and efficient approach to obtain optically pure 1,4-diols was established. The asymmetric oxidation of sulfides to sulfoxides with cumyl hydroperoxide in moderate yields and moderate to high enantioselectivities (up to 84%) catalyzed by chiral Ti/1,4-diols complexes has been achieved. A 76% ee value was obtained in the asymmetric synthesis of esomeprazole.

Key words

asymmetric oxidation - sulfide - sulfoxide - titanium - resolution

Full Text

References

1a Miller JA. Gross BA. Zhuravel MA. Jin W. Nguyen ST. Angew. Chem. Int. Ed. 2005, 44: 3885

1b Hiroi K. Watanabe K. Abe I. Koseki M. Tetrahedron Lett. 2001, 42: 7617

1c Massa A. Malkov AV. Kocovsky P. Scettria A. Tetrahedron Lett. 2003, 44: 7179

1d For reviews, see: Fernandez I. Khiar N. Chem. Rev. 2003, 103: 3651

1e Legros J. Dehli JR. Bolm C. Adv. Synth. Catal. 2005, 347: 19

2a Holland HL. Chem. Rev. 1988, 88: 473

2b Holland HL. Nat. Prod. Rep. 2001, 18: 171

3a Davis FA. Jenkins RH. Awad SB. Stringer OD. Watson WH. Galloy J. J. Am. Chem. Soc. 1982, 104: 5412

3b Davis FA. McCauley JP. Harakal JME. J. Org. Chem. 1984, 49: 1467

3c Davis FA. Lal SG. J. Org. Chem. 1988, 53: 5004

3d Lattanzi A. Iannece P. Scettri A. Tetrahedron: Asymmetry 2004, 15: 413

3e Lattanzi A. Iannece P. Scettri A. Tetrahedron: Asymmetry 2004, 15: 1779

3f Adam W. Korb MN. Roschmann KJ. Saha-Moller CR. J. Org. Chem. 1998, 63: 3423

4a Andersen KK. Gafield W. Papanikolaou NE. Foley JW. Perkins JI. J. Am. Chem. Soc. 1964, 86: 5637

4b Mioskowski C. Solladie G. Tetrahedron 1980, 35: 227

4c Solladie G. Hutt J. Girardin A. Synthesis 1987, 173

4d Khiar N. Araujo CS. Alcudia F. Fernandez I. J. Org. Chem. 2002, 67: 345

4e Delouvrie B. Fensterbank L. Najera F. Malacria M. Eur. J. Org. Chem. 2002, 3507

4f Ruano JLG. Alemparte C. Aranda MT. Zarzuelo MM. Org. Lett. 2003, 5: 75

4g Lu BZ. Jin F. Zhang Y. Wu X. Wald SA. Senanayake CH. Org. Lett. 2005, 7: 1465

5a Kagan HB. Dunach E. Nemecek C. Pitchen P. Samuel O. Zhao SH. Pure. Appl. Chem. 1985, 57: 1911

5b Zhao SH. Samuel O. Kagan HB. Tetrahedron 1987, 43: 5135

5c Di Furia F. Modena G. Seraglia R. Synthesis 1984, 325

5d Bortolini O. Di Furia F. Licini G. Modena G. Rossi M. Tetrahedron Lett. 1986, 27: 6257

6a Komatsu N. Hashizume M. Sugita T. Uemura S. J. Org. Chem. 1993, 58: 4529

6b Donnoli MI. Superchi S. Rosini C. J. Org. Chem. 1998, 63: 9392

6c Yamanoi Y. Imamoto T. J. Org. Chem. 1997, 62: 8560

6d Superchi S. Rosini C. Tetrahedron: Asymmetry 1997, 8: 349

6e Superchi S. Scafato P. Restaino L. Rosini C. Chirality 2008, 20: 592

6f Jia X. Li XS. Xu LJ. Li YM. Shi Q. Au-Yeung TTL. Yip CW. Yao XS. Chan ASC. Adv. Synth. Catal. 2004, 346: 723

6g Yamanoi Y. Imamoto T. J. Org. Chem. 1997, 62: 8560

7a Bolm C. Bienewald F. Angew. Chem., Int. Ed. 1995, 34: 2640

7b Ohta C. Shimizu H. Kondo A. Katsuki T. Synlett 2002, 161

7c Sun JT. Zhu CJ. Dai ZY. Yang MH. Pan Y. Hu HW. J. Org. Chem. 2004, 69: 8500

7d Kelly P. Lawrence SE. Maguire AR. Synlett 2006, 1569

7e Baltork IM. Hill M. Caggiano L. Jackson RFW. Synlett 2006, 3540

7f Bolm C. Bienewald F. Synlett 1998, 1327

7g Drago C. Caggiano L. Jackson R. Angew. Chem. Int. Ed. 2005, 44: 7221

7h Zeng Q. Wang H. Wang T. Cai Y. Weng W. Zhao Y. Adv. Synth. Catal. 2005, 347: 1933

7i Hinch M. Jacques O. Drago C. Cagglano L. Jackson RFW. Dexter C. Anson MS. Macdonald SJF. J. Mol. Catal. A: Chem. 2006, 251: 123

7j Blum SA. Bergman RG. Ellman JA. J. Org. Chem. 2003, 68: 150

7k Cogan D. Liu G. Kim K. Backes BJ. Ellman JA. J. Am. Chem. Soc. 1998, 120: 8011

7l Kelly P. Lawrence SE. Maguire AR. Eur. J. Org. Chem. 2006, 4500

8a Palucki M. Hanson P. Jacobsen EN. Tetrahedron Lett. 1992, 33: 7111

8b Noda K. Hosoya N. Irie R. Yamashita Y. Katsuki T. Tetrahedron 1994, 50: 9069

9a Legros J. Bolm C. Angew. Chem. Int. Ed. 2003, 42: 5487

9b Legros J. Bolm C. Angew. Chem. Int. Ed. 2004, 43: 4225

9c Legros J. Bolm C. Chem. Eur. J. 2005, 11: 1086

9d Egami H. Katsuki T. J. Am. Chem. Soc. 2007, 129: 8940

10 Miyazaki T. Katsuki T. Synlett 2003, 1046

11 Bonchio M. Licini G. Di Furia F. Mantovani S. Modena G. Nugent WA. J. Org. Chem. 1999, 64: 1326

12 Basak A. Barlan AU. Yamamoto H. Tetrahedron: Asymmetry 2006, 17: 508

13a Thakur VV. Sudalai A. Tetrahedron: Asymmetry 2003, 14: 407

13b Zhang Y. Sun JT. Zhu CJ. Chin. Chem. Lett. 2006, 17: 1173

14 Kelly P. Lawrence SE. Maguire AR. Synlett 2007, 1501

15 Matsumoto K. Yamaguchi T. Fujisaki J. Saito B. Katsuki T. Chem. Asian J. 2008, 3: 351

16 Scarso A. Strukul G. Adv. Synth. Catal. 2005, 347: 1227

17 Kantam ML. Prakash BV. Bharathi B. Reddy CV. J. Mol. Catal. A: Chem. 2005, 226: 119

18 Devine PN. Oh T. J. Org. Chem. 1992, 57: 386

19a Alexakis A. Mangeney P. Tetrahedron: Asymmetry 1990, 1: 477

19b Whitesell JK. Chem. Rev. 1989, 89: 1581

19c Halterman RL. Jan ST. Nimmons HL. Standlee DJ. Khan MA. Tetrahedron 1997, 53: 11257

19d Kim KS. Park JI. Ding P. Tetrahedron Lett. 1998, 39: 6471

20a Halterman RL. Zhu C. Chen Z. Dunlap MS. Khan MA. Nicholas KM. Organometallics 2000, 19: 3824

20b Halterman RL. Ramsey TM. Chen Z. J. Org. Chem. 1994, 59: 2642

20c Zhang Z. Zhu G. Jiang Q. Xiao D. Zhang X. J. Org. Chem. 1999, 64: 1774

20d Chen Z. Jiang Q. Zhu G. Xiao D. Cao P. Guo C. Zhang X. J. Org. Chem. 1997, 62: 4521

21 Zhu CJ. Yang MH. Sun JT. Zhu YH. Pan Y. Synlett 2004, 468

22 Chen Z. Eriks K. Halterman RL. Organometallics 1991, 10: 3449

23a Noda K. Hosoya N. Irie R. Yamashita Y. Katsuki T. Tetrahedron 1994, 50: 9609

23b Saito B. Katsuki T. Tetrahedron Lett. 2001, 42: 8333

23c Tanaka T. Saito B. Katsuki T. Tetrahedron Lett. 2002, 43: 3259

23d Wang XS. Wang XW. Guo HC. Wang Z. Ding KL. Chem. Eur. J. 2005, 11: 4078

23e Kagan HB. Fiaud JC. Top. Stereochem. 1988, 18: 249

24a Pitchen P. Dunach E. Deshmukh MN. Kagan HB. J. Am. Chem. Soc. 1984, 106: 8188

24b Capozzi MAM. Cardellicchio C. Naso F. Tortorella P. J. Org. Chem. 2000, 65: 2843

24c Palucki M. Hanson P. Jacobsen EN. Tetrahedron Lett. 1992, 33: 7111

24d Kokubo C. Katsuki T. Tetrahedron 1996, 52: 13895

25a Federsel HJ. Chirality 2003, 15: S128

26 Aldrich Handbook of Fine Chemicals and Laboratory Equipment Aldrich; Milwaukee: 2006-2007.