One-Pot Synthesis of 1,2,3-Triols
from Allylic Hydroperoxides and a Catalytic Amount of OsO4 in
Aqueous Acetone

Cemalettin Alp; Ufuk Atmaca; Murat Çelik; Mehmet Serdar Gültekin

doi:10.1055/s-0029-1217965

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 2009(17): 2765-2768
DOI: 10.1055/s-0029-1217965

LETTER

One-Pot Synthesis of 1,2,3-Triols from Allylic Hydroperoxides and a Catalytic Amount of OsO₄ in Aqueous Acetone

Cemalettin Alp, Ufuk Atmaca, Murat Çelik, Mehmet Serdar Gültekin*
Faculty of Sciences, Department of Chemistry, Atatürk University, 25240 Erzurum, Turkey
Fax: +90(442)2360948; e-Mail: gultekin@atauni.edu.tr;

Further Information

Publication History

Received 28 May 2009
Publication Date:
09 September 2009 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

Allylic hydroperoxides were converted into the corresponding triols in the presence of a catalytic amount of OsO₄. The present reaction involves regeneration of active osmium species by the hydroperoxide functionality and occurs in a diastereoselective manner to form triols in high yields. A plausible mechanism for the formation of 1,2,3-triols from allylic hydroperoxide is presented.

Key words

osmium tetraoxide - allylic hydroperoxide - triols - intramolecular oxygen transfer

References and Notes

1a Gültekin MS. Çelik M. Balci M. Curr. Org. Chem. 2004, 8: 1159

Google Scholar
1b Hudlicky T. Luna H. Price JD. Rulin F. J. Org. Chem. 1990, 55: 4683

Google Scholar
2a Kim KS. Park J. Ding P. Tetrahedron Lett. 1998, 39: 6471

Google Scholar
2b McCasland GE. Naumann MO. Duhram LJ. J. Org. Chem. 1996, 61: 3079

Google Scholar
2c Gültekin MS. Çelik M. Kurt E. Tanyeli C. Balci M. Tetrahedron: Asymmetry 2004, 15: 453

Google Scholar
3a Cha JK. Christ WJ. Kishi Y. Tetrahedron 1984, 40: 2247

Google Scholar
3b Gültekin MS. Salamci E. Balci M. Carbohydr. Res. 2003, 338: 1616

Google Scholar
3c Donohoe TJ. Moore PR. Beddoes RL. J. Chem. Soc., Perkin Trans. 1 1997, 43

Google Scholar
4a Burns PA. Foote CS. J. Am. Chem. Soc. 1974, 96: 4339

Google Scholar
4b Fenical W. Kearns DR. Radlich P. J. Am.Chem. Soc. 1969, 91: 7771

Google Scholar
4c Rubottom GM. Lopez NMI. Tetrahedron Lett. 1972, 21: 2423

Google Scholar
4d Bongini A. Cardillo G. Orena M. Porzi G. Sandri S. J. Org. Chem. 1982, 47: 4626

Google Scholar
4e Fernandez C. Gándara Z. Gómez G. Covelob B. Falla Y. Tetrahedron Lett. 2007, 48: 2939

Google Scholar
4f Brown RCD. Science of Synthesis Vol. 36: Thieme; Stuttgart: 2007. p.799

Google Scholar
5a Donohoe TJ. Moore PR. Waring J. Tetrahedron Lett. 1997, 38: 5027

Google Scholar
5b Whitehead DC. Travis BR. Borhan B. Tetrahedron Lett. 2006, 47: 3797

Google Scholar
5c Johansson M. Linden AA. Bäckvall J.-E.
J. Organomet. Chem. 2005, 690: 3614

Google Scholar
6a Trost BM. Dudash J. Hembre EJ. Chem. Eur. J. 2001, 7: 1619

Google Scholar
6b Plettenburg O. Adelt S. Vogel G. Altenbach HJ. Tetrahedron: Asymmetry 2000, 11: 1057

Google Scholar
6c Shing TKM. Tam EKW. J. Org. Chem. 1998, 63: 1547

Google Scholar
6d Knight JG. Tchabanenko K. Tetrahedron 2003, 59: 281

Google Scholar
6e Hudlicky T. Abboud KA. Entwistle DA. Fan R. Maurya R. Thorpe AJ. Bolonick J. Myers B. Synthesis 1996, 897

Google Scholar
7a Frimer AA. J. Org. Chem. 1977, 43: 3194

Google Scholar
7b Adam W. Epe B. Schiffmann D. Vargas F. Wild D. Angew. Chem. 1988, 100: 443

Google Scholar
7c Murty RS. Bio M. You Y. Tetrahedron Lett. 2009, 50: 1041

Google Scholar
9 Dang H. Davies AG. Davison IGE. Schiesser CH. J. Org. Chem. 1990, 55: 1432

Crossref Google Scholar
10a Chambers RD. Sandford G. Shah A. Synth. Commun. 1996, 10: 1861

Google Scholar
10b Van Sickle DE. Mayo FR. Arluck RM. J. Am. Chem. Soc. 1965, 87: 4824

Google Scholar
11a Donohoe TJ. Blades K. Moore PR. Waring MJ. Winter JJG. Helliwell M. Newcombe NJ. Stemp G. J. Org. Chem. 2002, 67: 7946

Google Scholar
11b Paulsen H. Brauer O. Chem. Ber. 2006, 110: 331

Google Scholar
12a Tong X. Xu J. Miao H. Yang G. Ma H. Zhang Q. Tetrahedron 2007, 63: 7634

Google Scholar
12b Mandel M. Hudlicky T. Synlett 1993, 418

Google Scholar
12c Dapurkar ES. Kawanami H. Komura K. Yokoyama T. Ikushima Y. Appl. Catal., A 2008, 346: 112

Google Scholar
13a Lee YJ. Lee K. Jung S. Jeon HB. Kim KS. Tetrahedron 2005, 61: 1987

Google Scholar
13b Paulsen H. Holger M. Tetrahedron Lett. 1972, 13: 3972

Google Scholar
14a Yoshihiko D. Shoji H. Tadao H. Yoshihisa I. Akira T. J. Chem. Soc., Perkin Trans. 2 1989, 275

Google Scholar
14b Yoshihisa I. Toshihiko U. Tadao H. J. Chem. Soc., Perkin Trans. 2 1984, 2053

Google Scholar
15a Paquette LA. Hartung RE. Hofferberth JE. Vilotijevic I. Yang J. J. Org. Chem. 2004, 69: 2454

Google Scholar
15b Jia C. Zhang Y. Zhang L. Tetrahedron: Asymmetry 2003, 14: 2195

Google Scholar
16a Matsushita Y. Sugamoto K. Nakama T. Matsui T.
J. Chem. Soc., Chem. Commun. 1995, 567

Google Scholar
16b Sugamoto K. Matsushita Y. Matsui T. J. Chem. Soc., Perkin Trans. 1 1998, 3989

Google Scholar
17a Blériot Y. Giroult A. Mallet J. Rodriguez E. Vogel P. Sinay P. Tetrahedron: Asymmetry 2002, 13: 2553

Google Scholar
17b Paquette LA. Zhang Y. J. Org. Chem. 2006, 71: 4353

Google Scholar
18a Foote CS. Burns P. J. Org. Chem. 1976, 41: 908

Google Scholar
18b Jeffery AM. Jerina DM. J. Am. Chem. Soc. 1972, 94: 4048

Google Scholar
19a Lee YT. Fisher JF. Bioorg. Chem. 2000, 28: 163

Google Scholar
19b Fulvia O. Francesca P. Tetrahedron: Asymmetry 1996, 7: 1033

Google Scholar
20a Parladar V. Gültekin MS. Çelik M. J. Chem. Res. 2006, 10

Google Scholar
20b Berrier C. Jounnetaud MP. Jacquesy JC. Kigabo F. Tetrahedron 1991, 47: 6681

Google Scholar
21a Pescarmona PP. Masters AF. Waal JC. Maschmeyer T. J. Mol. Catal. A: Chem. 2004, 220: 37

Google Scholar
21b Periasamy M. Kumar SS. Kumar NS. Tetrahedron Lett. 2008, 49: 4416

Google Scholar
21c Bäckvall J.-E. Modern Oxidation Methods John Wiley and Sons; New York: 2004.

Google Scholar
21d Arjona O. Dios A. Plumet J. Saez B. J. Org. Chem. 1995, 60: 4932

Google Scholar

8

Typical Procedure for the Formation of Triols
Allylic hydroperoxide (10 mmol) was dissolved in a mixture of H₂O-acetone (20 mL, 1:9) solution and OsO₄ (0.02 mmol, 5 mg) in acetone (5 mL) was added to the stirring solution of hydroperoxide. The mixture was stirred at r.t. at 22-65 h (examples in Table [¹] ). The reaction was monitored by TLC. The solution was evaporated (2.7˙10^-² bar, r.t.), and then the crude residue was directly purified by column chromatography on silica gel using EtOAc-hexanes as eluent to give the corresponding triols (Table [¹] ). rac -2,3-Dimethylbutane 1,2,3-Triol (2a)
^¹H NMR (200 MHz, CDCl₃): δ = 1.02 (s, 3 H), 1.18 (s, 3 H), 1.21 (s, 3 H), 3.44 (d, J = 11.3 Hz, 1 H), 3.83 (d, J = 11.3, 1 H) ppm. ^¹³C NMR (50 MHz, CDCl₃): δ = 22.1, 26.6, 27.2, 70.1, 77.5, 77.9 ppm. rac -Cyclopentane-1,2,3-triol (4a) ^¹H NMR (200 MHz, CD₃OD): δ = 1.39-1.83 (m, 2 H), 1.91-2.18 (m, 2 H), 3.69-3.79 (m, 1 H), 4.01-4.12 (m, 2 H) ppm. ^¹³C NMR (50 MHz, CD₃OD): δ = 31.5, 31.8, 74.6, 79.2, 82.7 ppm.
rac -Cyclopentane-1,2,3-triyl Triacetate (4b) ^¹H NMR (200 MHz, CDCl₃): δ = 1.49-1.61 (m, 1 H), 1.74-1.81 (m, 1 H), 2.02 (br s, 9 H, 3 CH₃), 2.23-2.44 (m, 2 H), 5.09-5.23 (m, 2 H), 5.28 (m, 1 H) ppm. ^¹³C NMR (50 MHz, CDCl₃): δ = 22.5, 22.6, 22.8, 28.6, 28.8, 74.1, 77.9, 78.4, 171.8, 171.9, 172.2 ppm. rac -Cyclohexane-1,2,3-triol (6a) ^¹H NMR (200 MHz, CD₃OD): δ = 1.20-1.87 (m, 6 H), 3.34 (dd, J = 2.7, 8.5 Hz, 1 H), 3.75 (m, 1 H), 4.01 (m, 1 H) ppm. ^¹³C NMR (50 MHz, CD₃OD): δ = 21.3, 33.5, 34.9, 72.9, 73.1, 79.1 ppm.
rac -Cyclohexane-1,2,3-triyl Triacetate (6b)
^¹H NMR (200 MHz, CDCl₃): δ = 1.57-1.97 (m, 6 H), 2.01 (s, 3 H), 2.05, (s, 3 H), 2.19, (s, 3 H), 4.90 (dd, J = 3.0, 9.1 Hz, 1 H), 5.05 (m, 1 H), 5.32 (m, 1 H) ppm. ^¹³C NMR (50 MHz, CDCl₃): δ = 20.3, 22.5, 22.8, 23.9, 29.9, 30.8, 71.9, 72.3, 74.4, 168.1, 171.8, 171.9 ppm.
rac -Cycloheptane-1,2,3-triol (8a): ^¹H NMR (200 MHz, CD₃OD): δ = 1.45-1.88 (m, 8 H), 3.55 (dd, J = 2.5, 7.1 Hz, 2 H), 3.70 (m, 1 H), 3.96 (m, 1 H) ppm.^¹³C NMR (50 MHz, CD₃OD): δ = 25.4, 26.3, 33.4, 35.8, 74.6, 75.3, 82.2 ppm.
rac -Cycloheptane-1,2,3-triyl Triacetate (8b): ^¹H NMR (200 MHz, CDCl₃): δ = 1.42-1.66 (m, 8 H), 2.02 (s, 3 H), 1.99 (s, 3 H), 1.97 (s, 3 H), 4.86 (dd, J = 2.0, 4.2, 1 H), 4.95 (m, 1 H), 5.06 (m, 1 H) ppm. ^¹³C NMR (50 MHz, CDCl₃): δ = 22.7, 22.8, 22.9, 23.8, 24.0, 29.7, 29.9, 73.9, 74.4, 78.05, 171.8 (2 C), 171.9 ppm.
rac -Cyclooctane-1,2,3-triol (10a): ^¹H NMR (200 MHz, CD₃OD): δ = 1.55-1.90 (m, 10 H), 3.65 (dd, J = 2.4, 8.5 Hz, 1 H), 3.79 (m, 1 H), 3.96 (m, 1 H) ppm. ^¹³C NMR (50 MHz, CD₃OD): δ = 26.1, 27.8, 29.9, 34.0, 36.1, 73.8, 74.8, 80.8 ppm.
rac -Cyclooctane-1,2,3-triyl Triacetate (10b): ^¹H NMR (200 MHz, CDCl₃): δ = 1.45-2.01 (m, 10 H), 1.93 (s, 3 H), 1.96 (s, 3 H), 1.97 (s, 3 H), 4.92-5.23 (m, 3 H) ppm. ^¹³C NMR (50 MHz, CDCl₃): δ = 22.9, 24.3, 25.6, 26.5, 28.2, 29.9, 30.9, 31.7, 73.4, 75.3, 76.4, 171.8, 172.0, 172.1 ppm.
rac -1,2,3,4-Tetrahydronaphthalene-1,2,3-triol (12a): ^¹H NMR (200 MHz, CD₃OD): δ = 7.18 (m, 4 H), 2.56-3.09 (m, 2 H), 4.64 (m, 1 H), 4.02 (m, 1 H), 3.61 (1 H) ppm. ^¹³C NMR (50 MHz, CD₃OD): δ = 38.9, 68.9, 72.8, 76.5, 128.5, 128.9, 129.7, 130.3, 137.3, 138.5 ppm.
rac -2,3,4-Trihydroxy-4-methylcyclohexanone (14a): ^¹H NMR (200 MHz, CDCl₃): δ = 4.22 (d, J = 5.7 Hz, 1 H), 3.72 (d, J = 5.7 Hz, 1 H), 2.22-1.84 (m, 4 H), 1.27 (s, 3 H) ppm. ^¹³C NMR (50 MHz, CDCl₃): δ = 28.5, 36.3, 37.4, 74.5, 75.8, 79.9, 209.8 ppm.