Cyclopropenium-Activated DMSO for Swern-Type Oxidation

Tianfo Guo; Yu Gao; Zhenjiang Li; Jingjing Liu; Kai Guo

doi:10.1055/s-0037-1611183

Synlett, Table of Contents

Synlett 2019; 30(03): 329-332
DOI: 10.1055/s-0037-1611183

letter

Cyclopropenium-Activated DMSO for Swern-Type Oxidation

Tianfo Guo

,

Yu Gao

,

Zhenjiang Li*

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, 30 Puzhu Road South, Nanjing 211816, P. R. of China Email: guok@njtech.edu.cn Email: zjli@njtech.edu.cn

,

Jingjing Liu

,

Kai Guo*

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, 30 Puzhu Road South, Nanjing 211816, P. R. of China Email: guok@njtech.edu.cn Email: zjli@njtech.edu.cn

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Abstract

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Abstract

Swern oxidation is widely used to convert alcohols into their corresponding carbonyl compounds. However, the conventional method with use of the volatile oxalyl chloride as an activator requires the reaction to be conducted below −60 °C. We discovered that 3,3-dichloro-1,2-diphenylcyclopropene (DDC) can be used as a new activator for Swern-type oxidations of alcohols, which can be conducted at −20 °C. This new protocol features mild and fast reactions with easy operation. Furthermore, the activator DDC is easy to handle, and diphenylcyclopropenone can be recovered quantitively. This new type of Swern oxidation shows a broad scope of substrates including benzylic, allylic, aliphatic, and biobased alcohols, and gives high yields of up to 93%.

Key words

alcohols - carbonyl compounds - cyclopropenium ion - geminal dichloro compounds - Swern oxidation

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References

References and Notes
1 Haines AH. In Methods for Oxidation of Organic Compounds . Haines AH. Academic Press; New York: 1988: 5

2a Mancuso AJ, Swern D. Synthesis 1981; 165
2b Tidwell TT. Synthesis 1990; 857

3 Albright JD, Goldman L. J. Am. Chem. Soc. 1965; 87: 4214
4 Onodera K, Hirano S, Kashimura N. J. Am. Chem. Soc. 1965; 87: 4651
5 Parikh JR, Doering W.v.E. J. Am. Chem. Soc. 1967; 89: 5505
6 Omura K, Sharma A, Swern D. J. Org. Chem. 1976; 41: 957
7 Mancuso AJ, Huang S.-L, Swern D. J. Org. Chem. 1978; 43: 2480

8a De Luca L, Giacomelli G, Porcheddu A. J. Org. Chem. 2001; 66: 7907
8b Bisai A, Chandrasekhar M, Singh VK. Tetrahedron Lett. 2002; 43: 8355
8c Nguyen TV, Hall M. Tetrahedron Lett. 2014; 55: 6895

9 Gao Y, Liu J, Li Z, Guo T, Xu S, Zhu H, Wei F, Chen S, Gebru H, Guo K. J. Org. Chem. 2018; 83: 2040
10 Breslow R. J. Am. Chem. Soc. 1957; 79: 5318

11a Komatsu K, Kitagawa T. Chem. Rev. 2003; 103: 1371
11b Lyons DJ. M, Crocker RD, Blümel M, Nguyen TV. Angew. Chem. Int. Ed. 2017; 56: 1466
11c D’yakonov IA, Rafael RK. Russ. Chem. Rev. 1967; 36: 557
11d Yoshida Z.-i. Top. Curr. Chem. 1973; 40: 47
11e Krivun SV, Alferova OF, Sayapina SV. Russ. Chem. Rev. 1974; 43: 835

12a Kelly BD, Lambert TH. J. Am. Chem. Soc. 2009; 131: 13930
12b Vanos CM, Lambert TH. Angew. Chem. Int. Ed. 2011; 50: 12222

13 Vanos CM, Lambert TH. Chem. Sci. 2010; 1: 705
14 Hardee DJ, Kovalchuke L, Lambert TH. J. Am. Chem. Soc. 2010; 132: 5002
15 Li L, Ni C, Wang F, Hu J. Nat. Commun. 2016; 7: 13320
16 Stach T, Dräger J, Huy PH. Org. Lett. 2018; 20: 2980
17 NMR spectra of 1: ¹H NMR (400 MHz, CDCl₃): δ 8.23–8.20 (m, 4 H), 7.75–7.70 (m, 2 H), 7.68–7.64 (m, 4 H). ¹³C NMR (100 MHz, CD₃CN): δ 131.5, 129.9, 129.3, 125.2, 123.0.
18 General procedureA solution of DMSO (5.0 equiv) in dichloromethane (DCM) was added to a solution of 1 (1.5 equiv) in DCM at –30 °C, and the mixture was stirred for 20 min at the same temperature. Then, a solution of 2-phenylethanol (1.0 equiv) in DCM was added and continuously stirred for another 20 min before the dropwise addition of Et₃N (5.0 equiv). The mixture was subsequently left to warm to room temperature and concentrated under reduced pressure. The product was analyzed by gas chromatography (GC) and isolated by column chromatography.

19a Corey EJ, Kim CU. J. Am. Chem. Soc. 1972; 94: 7586
19b Omura K, Swern D. Tetrahedron 1978; 34: 1651

20 Tojo G, Fernandez MI. Oxidation of Alcohols to Aldehydes and Ketones . Springer; New York: 2006
21 Hünig S, Kiessel M. Chem. Ber. 1958; 91: 380

22a Walba DM, Thurmes WN, Haltiwanger RC. J. Org. Chem. 1988; 53: 1046
22b Evans DA, Polniaszek RP, DeVries KM, Guinn DE, Mathre DJ. J. Am. Chem. Soc. 1991; 113: 7613
22c Evans DA, Gage JR, Leighton JL. J. Am. Chem. Soc. 1992; 114: 9434

23 Mancuso AJ, Brownfain DS, Swern D. J. Org. Chem. 1979; 44: 4148
24 Nguyen TV, Bekensir A. Org. Lett. 2014; 16: 1720

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