Sulfuric Acid-Promoted Oxidation of Benzylic Alcohols to Aromatic Aldehydes in Dimethyl Sulfoxide: An Efficient Metal-Free Oxidation Approach

Ehsan Sheikhi; Mehdi Adib; Morteza Akherati Karajabad; Seyed Jamal Addin Gohari

doi:10.1055/s-0037-1609149

Synlett, Inhaltsverzeichnis

Synlett 2018; 29(07): 974-978
DOI: 10.1055/s-0037-1609149

letter

Sulfuric Acid-Promoted Oxidation of Benzylic Alcohols to Aromatic Aldehydes in Dimethyl Sulfoxide: An Efficient Metal-Free Oxidation Approach

Ehsan Sheikhi*

^aSchool of Chemistry, College of Science, University of Tehran, PO Box 14155-6455, Tehran, Iran eMail: ehsan.sheikhi@gmail.com eMail: madib@khayam.ut.ac.ir

,

Mehdi Adib*

^aSchool of Chemistry, College of Science, University of Tehran, PO Box 14155-6455, Tehran, Iran eMail: ehsan.sheikhi@gmail.com eMail: madib@khayam.ut.ac.ir

,

Morteza Akherati Karajabad

^aSchool of Chemistry, College of Science, University of Tehran, PO Box 14155-6455, Tehran, Iran eMail: ehsan.sheikhi@gmail.com eMail: madib@khayam.ut.ac.ir

,

Seyed Jamal Addin Gohari

^bDepartment of Chemistry, Imam Hossein University, Tehran, Iran

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

An efficient metal-free oxidation of benzylic alcohols to aromatic aldehydes is described. Heating a solution of the benzylic alcohol in DMSO in the presence of H₂SO₄ afforded the corresponding aldehyde in excellent yield. This oxidation reaction, which proceeds with a short reaction time and no side products, is akin to the Pfitzner–Moffatt oxidation, but without the need for N,N′-dicyclohexylcarbodiimide.

Key words

benzylic alcohols - aromatic aldehydes - sulfuric acid - dimethyl sulfoxide - oxidation

Volltext

Referenzen

References and Notes

1a Bowden K. Heilbron IM. Jones ER. H. Weedon BC. L. J. Chem. Soc. 1946; 39
1b Heilbron SI. Jones ER. H. Sondheimer F. J. Chem. Soc. 1949; 604

2a Collins JC. Hess WW. Frank FJ. Tetrahedron Lett. 1968; 9: 3363
2b Collins JC. Hess WW. Org. Synth. Coll. Vol. VI . Wiley; London: 1988: 644

3 Corey EJ. Suggs JW. Tetrahedron Lett. 1975; 16: 2647
4 Corey EJ. Schmidt G. Tetrahedron Lett. 1979; 20: 399

5a Dess DB. Martin JC. J. Org. Chem. 1983; 48: 4155
5b Dess DB. Martin JC. J. Am. Chem. Soc. 1991; 113: 7277

6a Corey EJ. Palani A. Tetrahedron Lett. 1995; 36: 7945
6b Frigerio M. Santagostino M. Sputore S. Palmisano G. J. Org. Chem. 1995; 60: 7272

7a Zhdankin VV. Stang PJ. Chem. Rev. 2002; 102: 2523
7b Stang PJ. J. Org. Chem. 2003; 68: 2997
7c Wirth T. Angew. Chem. Int. Ed. 2005; 44: 3656

8a Brünjes M. Sourkouni-Argirusi G. Kirschning A. Adv. Synth. Catal. 2003; 345: 635
8b Liu R. Liang X. Dong C. Hu X. J. Am. Chem. Soc. 2004; 126: 4112
8c Gamez P. Arends IW. C. E. Sheldon RA. Reedijk J. Adv. Synth. Catal. 2004; 346: 805
8d Liu R. Dong C. Liang X. Wang X. Hu X. J. Org. Chem. 2005; 70: 729
8e Xie Y. Mo W. Xu D. Shen Z. Sun N. Hu B. Hu X. J. Org. Chem. 2007; 72: 4288
8f Wang X. Liu R. Jin Y. Liang X. Chem. Eur. J. 2008; 14: 2679
8g Kantam ML. Pal U. Sreedhar B. Bhargava S. Iwasawa Y. Tada M. Choudary BE. Adv. Synth. Catal. 2008; 350: 1225

9 Corey EJ. Kim CU. J. Am. Chem. Soc. 1972; 94: 7586

10a Oppenauer RV. Recl. Trav. Chim. Pays-Bas 1937; 56: 137
10b Graves CR. Zeng B.-S. Nguyen ST. J. Am. Chem. Soc. 2006; 128: 12596

11a Fatiadi AJ. Synthesis 1976; 65
11b Fatiadi AJ. Synthesis 1976; 133
11c Lou J.-D. Xu Z.-N. Tetrahedron Lett. 2002; 43: 6149
11d Alhumaimess M. Lin Z. He Q. Lu L. Dimitratos N. Dummer NF. Conte M. Taylor SH. Bartley JK. Kiely CJ. Hutchings GJ. Chem. Eur. J. 2014; 20: 1701

12a Griffith WP. Ley SV. Whitcombe GP. White AD. J. Chem. Soc., Chem. Commun. 1987; 1625
12b Ley SV. Norman J. Griffith WP. Marsden SP. Synthesis 1994; 639

13a Uozumi Y. Nakao R. Angew. Chem. Int. Ed. 2003; 42: 194
13b Della Pina C. Falletta E. Rossi M. J. Catal. 2008; 260: 384
13c Mizoguchi H. Uchida T. Ishida K. Katsuki T. Tetrahedron Lett. 2009; 50: 3432
13d Zhou X.-T. Ji H.-B. Liu S.-G. Tetrahedron Lett. 2013; 54: 3882
13e Devari S. Deshidi R. Kumar M. Kumar A. Sharma S. Rizvi M. Kushwaha M. Gupta AP. Shah BA. Tetrahedron Lett. 2013; 54: 6407
13f Han L. Xing P. Jiang B. Org. Lett. 2014; 16: 3428
13g Liu C. Fang Z. Yang Z. Li Q. Guo S. Zhang K. Ouyang P. Guo K. Tetrahedron Lett. 2015; 56: 5973
13h Liu C. Fang Z. Yang Z. Li Q. Guo S. Guo K. RSC Adv. 2015; 5: 79699
13i Saffar-Teluri A. RSC Adv. 2015; 5: 70577
13j Samanta S. Biswas P. RSC Adv. 2015; 5: 84328

14 Pfitzner KE. Moffatt JG. J. Am. Chem. Soc. 1963; 85: 3027
15 Parikh JR. Doering W. vonE. J. Am. Chem. Soc. 1967; 89: 5505

16a Omura K. Swern D. Tetrahedron 1978; 34: 1651
16b Mancuso AJ. Brownfain DS. Swern D. J. Org. Chem. 1979; 44: 4148

17a Albright JD. Goldman L. J. Am. Chem. Soc. 1965; 87: 4214
17b Albright JD. Goldman L. J. Am. Chem. Soc. 1967; 89: 2416

18 Onodera K. Hirano S. Kashimura N. J. Am. Chem. Soc. 1965; 87: 4651
19 Liu H.-J. Nyangulu JM. Tetrahedron Lett. 1988; 29: 3167
20 Li C. Xu Y. Lu M. Zhao Z. Liu L. Zhao Z. Cui Y. Zheng P. Ji X. Gao G. Synlett 2002; 2041

21a Choudhury LH. Parvin T. Khan AT. Tetrahedron 2009; 65: 9513
21b Inagaki M. Matsumoto S. Tsuri T. J. Org. Chem. 2003; 68: 1128
21c Majetich G. Hicks R. Reister S. J. Org. Chem. 1997; 62: 4321

22 Aldehydes 2a–n; General Procedures Protocol A: A mixture of the benzylic alcohol 1 (1 mmol) and 98% H₂SO₄ (1 mmol) in DMSO (3 mL) was stirred for the appropriate time under reflux conditions. The mixture was then cooled to r.t., and brine (4 mL) was added. The organic phase was extracted with CH₂Cl₂ (6 mL), and the organic layer was dried (Na₂SO₄), filtered, and concentrated under reduced pressure. In all cases, the reaction products were obtained with high purity, and did not require further purification by distillation or column chromatography. Protocol B: A mixture of benzylic alcohol (1 mmol) and 98% H₂SO₄ (0.5 mmol) in DMSO (3 mL) was stirred for the appropriate reaction time under reflux conditions. The reaction mixture was then worked up as described in Protocol A.