Green Synthesis of Haloformates from Olefins Using Formic Acid as Reactant, Protonic Acid, and Solvent

Ligeng Wang; Hualong Zhang; Qin Yu; Chun Feng; Jun Hu

doi:10.1055/s-0037-1610028

Synlett, Inhaltsverzeichnis

Synlett 2018; 29(12): 1611-1616
DOI: 10.1055/s-0037-1610028

letter

Green Synthesis of Haloformates from Olefins Using Formic Acid as Reactant, Protonic Acid, and Solvent

Ligeng Wang *

College of Chemical Engineering, Zhejiang University of Technology, Zhejiang 310014, P. R. of China eMail: wanglg@zjut.edu.cn eMail: hjzjut@zjut.edu.cn

,

Hualong Zhang

College of Chemical Engineering, Zhejiang University of Technology, Zhejiang 310014, P. R. of China eMail: wanglg@zjut.edu.cn eMail: hjzjut@zjut.edu.cn

,

Qin Yu

College of Chemical Engineering, Zhejiang University of Technology, Zhejiang 310014, P. R. of China eMail: wanglg@zjut.edu.cn eMail: hjzjut@zjut.edu.cn

,

Chun Feng

College of Chemical Engineering, Zhejiang University of Technology, Zhejiang 310014, P. R. of China eMail: wanglg@zjut.edu.cn eMail: hjzjut@zjut.edu.cn

,

Jun Hu*

College of Chemical Engineering, Zhejiang University of Technology, Zhejiang 310014, P. R. of China eMail: wanglg@zjut.edu.cn eMail: hjzjut@zjut.edu.cn

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Abstract

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Abstract

Bromoformates and iodoformates are successfully synthesized in high yields with regioselectivity and stereoselectivity by using ZnAl-BrO₃ ^– layered double hydroxides (LDHs) and KX (X = Br, I) in the presence of formic acid (HCOOH). The protocol exploits the versatile function of formic acid as solvent, nucleophilic reagent, and acidic medium simultaneously, simplifying the reaction and separation of the products.

Key words

olefins - formic acid - bromoformates - iodoformates - regioselectivity - stereoselectivity

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Referenzen

References and Notes

1a Dewkar GK. Narina SV. Sudalai A. Org. Lett. 2003; 5: 4501
1b Damin B. Garapon J. Sillion B. Synthesis 1981; 362
1c Damin B. Garapon J. Sillion B. Tetrahedron Lett. 1980; 21: 1709

2a Macharla AK. Nappunni RC. Nama N. Tetrahedron Lett. 2012; 53: 1401
2b Phukan P. Chakraborty P. Kataki DJ. J. Org. Chem. 2006; 71: 7533
2c Taber DF. Liang JL. J. Org. Chem. 2007; 72: 431
2d Yeung YY. Gao X. Corey EJ. J. Am. Chem. Soc. 2006; 128: 9644

3a Tripathy N. k. Georg G. I. 2004; 45: 5309
3b Buynak JD. Mathew J. Rao MN. J. Chem. Soc., Chem. Commun. 1986; 12: 941
3c Thiem J. Gerken MJ. Carbohydr. Chem. 1982; 1: 229
3d Liang J. Moher ED. Moore RE. Hoard DW. J. Org. Chem. 2000; 65: 3143

4a Anderson JC. Headley C. Stapleton PD. Taylor PW. Tetrahedron 2005; 61: 7703
4b Li L. Chan TH. Org. Lett. 2001; 3: 739
4c Larivée A. Unger JB. Thomas M. Wirtz C. Dubost C. Handa S. Fürstner A. Angew. Chem. Int. Ed. 2011; 50: 304

5 Kolb HC. Sharpless KB. Tetrahedron 1992; 48: 10515

6a Hamm S. Henning L. Findeisen M. Müller D. Welzel P. Tetrahedron 2000; 56: 1345
6b Suginome H. Wang JB. Bull. Chem. Soc. Jpn. 1989; 62: 193

7a Glukhovtsev MN. Pross A. Radom L. J. Am. Chem. Soc. 1995; 117: 9012
7b Xiao MY. Ren DD. Xu LB. Li SS. Yu LP. Xiao J. Org. Lett. 2017; 19: 5724
7c Ortiz R. Herrera RP. Molecules 2017; 22: 574
7d Zhu Y. Mei HB. Han JL. Soloshonok VA. Zhou J. Pan Y. J. Org. Chem. 2017; 82: 13663
7e Miralles N. Gomez JE. Kleij AW. Fernandez E. Org. Lett. 2017; 19: 6096

8 De Souza AV. A. Mendonca GF. Bernini RB. De Mattos MC. S. J. Braz. Chem. Soc. 2007; 18: 1575
9 Dalton DR. Smith RC. J. Jones DG. Tetrahedron 1970; 26: 575
10 Saikia I. Krishna KR. Phukan P. Tetrahedron Lett. 2012; 53: 758
11 Podgoršek A. Eissen M. Fleckenstein J. Stavber S. Zupan M. Iskra J. Green Chem. 2009; 11: 120
12 Mameda N. Peraka S. Macharla AK. Marri MR. Kodumuri S. Nama N. Tetrahedron Lett. 2014; 55: 3926
13 Chevella D. Mameda N. Macharla AK. Peraka S. Marri MR. Kodumuri S. Nama N. Synth. Commun. 2016; 13: 1133

14a Niizato H. Ueno Y. Takemura S. Chem. Pharm. Bull. 1972; 20: 2707
14b Ueno Y. Yamasaki A. Terauchi H. Takemura S. Chem. Pharm. Bull. 1974; 22: 1646

15a Ganboa I. Palomo C. Synth. Commun. 1983; 13: 941
15b Li XK. Ho B. Lim DS. W. Zhang YG. Green Chem. 2017; 19: 914
15c Zhang F. Lu Q. Yue XX. Zuo BQ. Qin MD. Li F. Kaplan DL. Zhang XG. Acta Biomater. 2015; 12: 139
15d Schettini AR. A. Peres RC. D. Soares BG. Synth. Met. 2009; 159: 1491
15e Schueren LV. D. Steyaert I. Schoenmaker BD. Clerck KD. Carbohydr. Polym. 2012; 88: 1221

16a Kozar LG. Clark RD. Heathcock CH. J. Org. Chem. 1977; 42: 1386
16b Kleinfelter DC. Schleyer P. vR. Org. Synth. 1962; 42: 79
16c Kaulen J. Angew. Chem. Int. Ed. Engl. 1987; 26: 773
16d Wang L. Floreancig PE. Org. Lett. 2004; 6: 4207

17a Wang LG. Zheng FX. Jiang CX. Ni ZM. J. Chin. Ceram. Soc. 2015; 43: 672
17b Yang MS. Gu LH. Yang B. Wang L. Sun ZY. Zheng JY. Appl. Surf. Sci. 2017; 426: 185
17c Djebbi MA. Elabed A. Bouaziz Z. Sadiki M. Elabed S. Namour P. Jaffrezic-Renault N. Amare AB. H. Int. J. Pharm. 2016; 515: 422

18a Veeraiah T. Sondu S. Int. J. Chem. Sci. 2007; 5: 911
18b Imbri D. Netz N. Kucukdisli M. Kammer LM. Jung P. Kretzschmann A. Opatz T. J. Org. Chem. 2014; 79: 11750
18c Karama U. Mahfouz R. Al-Othman Z. Warad I. Almansour A. Synth. Commun. 2013; 43: 893
18d Solladié N. Gross M. Tetrahedron Lett. 1999; 40: 3359

19a Song S. Huang XQ. Liang YF. Tang CH. Li XW. Jiao N. Green Chem. 2015; 17: 2727
19b Dong JJ. Fernández-Fueyo E. Li JB. Guo Z. Renirie R. Wever R. Hollmann F. Green Chem. 2017; 53: 6207
19c Lodh RS. Borah AJ. Phukan P. Indian. J. Chem. 2014; 53B, 1425

20a Adimurthy S. Ghosh S. Patoliya PU. Ramachandraiah G. Agrawal M. Gandhi MR. Upadhyay SC. Ghosh PK. Ranu BC. Green Chem. 2008; 10: 232
20b Cortes CE. S. Faria RB. Inorg. Chem. 2004; 43: 1395

21a Zheng CY. Slebocka-Tilk H. Nagoraski RW. Alvarado L. Brown RS. J. Org. Chem. 1993; 58: 2122
21b Heasley VL. Shellhamer DF. Iskilian JA. Street DL. J. Org. Chem. 1978; 43: 3139
21c Vardhan HB. Bach RD. J. Org. Chem. 1992; 57: 4948
21d Slebocka-Tilk H. Nagorski SM. R. W. Brown PT. R. S. McDonald R. J. Am. Chem. Soc. 1995; 117: 8769
21e Chiappe C. Rubertis AD. Jaber A. Lenoir D. Wattenbach C. Pomelli CS. J. Org. Chem. 2002; 67: 7066
21f McClendon E. Omollo AO. Valente EJ. Hamme AT. Tetrahedron Lett. 2009; 50: 533

22 Representative Procedure for the Synthesis of Bromoformate 2f Substrate (1f, 324.4 mg, 2 mmol), KBr (190.4 mg, 1.6 mmol), formic acid (10 mL) were added to a 50 mL three-necked flask, and KBr was absolutely dissolved in the mixture with proper stirring at room temperature. After ZnAl-BrO₃ ^–-LDHs (0.8 g) was added to the mixture, the reaction system was stirred at 40 °C with use of a reflux condenser in a water bath until the substrate completely disappeared (monitored by TLC). The molecular bromine was treated with sodium bisulfite solution right away. The solid phase ZnAl-BrO₃ ^–-LDHs was removed by centrifugation. Furthermore, the dichloromethane (3 × 5 mL) used for washing the ZnAl-BrO₃ ^–-LDHs was merged into the liquid mixture after centrifugation. Then, the products were extracted into the organic phase with dichloromethane (3 × 10 mL) and H₂O (30 mL). The organic phase was dried with sodium sulfate and concentrated in vacuum. The crude product was purified by column chromatography on silica gel. 2-Bromo-1-(4-acetoxylphenyl)ethyl formate (2f) Yield: 493.8 mg, 86%. Colorless oil. ¹H NMR (500 MHz, CDCl₃): δ = 8.15 (s, 1 H), 7.42–7.39 (m, 2 H), 7.14–7.12 (m, 2 H), 6.11 (dd, J = 8.3, 4.5 Hz, 1 H), 3.68 (dd, J = 11.0, 8.4 Hz, 1 H), 3.61 (dd, J = 11.0, 4.5 Hz, 1 H), 2.31 (s, 3 H) ppm. ¹³C NMR (126 MHz, CDCl₃): δ = 169.16, 159.52, 151.09, 134.49, 127.84, 122.00, 74.04, 33.51, 21.07 ppm. HRMS (ESI): m/z calcd for C₁₁H₁₁BrO₄ [M + H]⁺: 286.9919; found: 286.9917.

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