Copper Porphyrin Catalyzed C(sp³)–H Activation via Cross-Dehydrogenative Coupling: Facile Transformation of Aldehydes to Esters

Abstract

Copper porphyrin catalyzed alkane C–H bond functionalization with aldehydes via cross-dehydrogenative coupling (CDC) using DTBP oxidant has been firstly described in nonsolvents or nonadditives system. Different aryl/heteroaryl carboxylic esters were obtained in good to excellent yields depending on the aldehyde derivatives. This CDC reaction catalyzed by copper porphyrin has the advantages of shorter reaction time, lower reaction temperature, and catalyst loading as well as the aerobic reaction atmosphere.

Key words

copper porphyrin - aldehydes - alkanes - cross-dehydrogenative coupling - C–H activation

• References and Notes

• 1 Moaddeli A, Rousta M, Shekouhy M, Khalili D, Samadi M, Khalafi-Nezhad A. Asian J. Org. Chem. 2019; 8: 356
• 2 Liu RX, Heiss EH, Waltenberger B, Blazevic T, Schachner D, Jiang BH, Krystof V, Liu WH, Schwaiger S, Pena-Rodriguez LM, Breuss JM, Stuppner H, Dirsch VM, Atanasov AG. Mol. Nutr. Food Res. 2018; 62: 1700860
• 3 Bhatt P, Zhou X, Huang Y, Zhang W, Chen S. J. Hazard. Mater. 2021; 411: 125026
• 4 Olgierd B, Kamila Ż, Anna B, Emilia M. Molecules 2021; 26: 1335
• 5 Dey S, Gadakh SK, Sudalai A. Org. Biomol. Chem. 2015; 13: 10631
• 6 Vedaraman N, Puhan S, Nagarajan G, Ramabrahmam BV, Velappan KC. Ind. Crops Prod. 2012; 36: 282
• 7 Wu Z, Li Y, Wang M, Li J, Wang Z. J. Dispersion Sci. Technol. 2020; 42: 1163
• 8 Khan Z, Javed F, Shamair Z, Hafeez A, Fazal T, Aslam A, Zimmerman WB, Rehman F. J. Ind. Eng. Chem. 2021; 103: 80
• 9 Junzo Otera JN. Esterification 2010; 193
• 10 Ekoue-Kovi K, Wolf C. Chem. Eur. J. 2008; 14: 6302
• 11a Gandhi S. Org. Biomol. Chem. 2019; 17: 9683
• 11b Liu C, Yuan J, Gao M, Tang S, Li W, Shi R, Lei A. Chem. Rev. 2015; 115: 12138
• 12a Wei W, Zhang C, Xu Y, Wan X. Chem. Commun. 2011; 47: 10827
• 12b Wang Q, Zheng H, Chai W, Chen DY, Zeng XJ, Fu RZ, Yuan RX. Org. Biomol. Chem. 2014; 12: 6549
• 13 Huang J, Li LT, Li HY, Husan E, Wang P, Wang B. Chem. Commun. 2012; 48: 10204
• 14 Dagar N, Singh S, Roy SR. Asian J. Org. Chem. 2021; 10: 2238
• 15 Zhu F, Wang Z.-X. Tetrahedron 2014; 70: 9819
• 16a Rout SK, Guin S, Ali W, Gogoi A, Patel BK. Org. Lett. 2014; 16: 3086
• 16b Wang CY, Song RJ, Wei WT, Fan JH, Li JH. Chem. Commun. 2015; 51: 2361
• 16c Jash U, Chakraborty G, Sinha S, Sikari R, Mondal R, Paul ND. Asian J. Org. Chem. 2018; 7: 1681
• 17 Rout SK, Guin S, Ghara KK, Banerjee A, Patel BK. Org. Lett. 2012; 14: 3982
• 18 Zhao J, Fang H, Han J, Pan Y. Org. Lett. 2014; 16: 2530
• 19 Pandey V, Jain D, Pareek N, Gupta I. Inorg. Chim. Acta 2020; 502: 119339
• 20 Feng L, Wang K.-Y, Joseph E, Zhou H.-C. Trends Chem. 2020; 2: 555
• 21 Chen Y, Luo R, Xu Q, Jiang J, Zhou X, Ji H. ChemSusChem 2017; 10: 2534
• 22 Casali E, Gallo E, Toma L. Inorg. Chem. 2020; 59: 11329
• 23 Lu Y, Huang CY, Liu C, Guo Y, Chen QY. Eur. J. Org. Chem. 2018; 2082
• 24 Singh R, Mukherjee A. ACS Catal. 2019; 9: 3604
• 25 van den Boomen OI, Coumans RG. E, Akeroyd N, Peters TP. J, Schlebos PP. J, Smits J, de Gelder R, Elemans JA. A. W, Nolte RJ. M, Rowan AE. Tetrahedron 2017; 73: 5029
• 26 Srour H, Jalkh J, Le Maux P, Chevance S, Kobeissi M, Simonneaux G. J. Mol. Catal. A: Chem. 2013; 370: 75
• 27 Yang XL, Zou C, He Y, Zhao M, Chen B, Xiang S, O'Keeffe M, Wu CD. Chem. Eur. J. 2014; 20: 1447
• 28 Sheng W.-B, Chen T.-Q, Zhang M.-Z, Tian M, Jiang G.-F, Guo C.-C. Tetrahedron Lett. 2016; 57: 1641
• 29a Wang H.-H, Wen W.-H, Zou H.-B, Cheng F, Ali A, Shi L, Liu H.-Y, Chang C.-K. New J. Chem. 2017; 41: 3508
• 29b Wen W.-H, Xie A.-N, Wang H.-H, Zhang D.-X, Ali A, Ying X, Liu H.-Y. Tetrahedron 2017; 73: 7169
• 29c Xiong M.-F, Ali A, Akram W, Zhang H, Si L.-P, Liu H.-Y. Catal. Commun. 2019; 125: 93
• 30 Cyclohex-2-en-1-yl benzoate (1a) CuTPP (3.4 mg, 0.005 mmol), benzaldehyde (1, 50 μL, 0.5 mmol), cyclohexane (a, 1.0 mL), and DTBP (2.75 mmol, 485 μL) were added to a 15 mL Schlenk tube containing a magneton, which were stirred at 120 °C for 12 h under sealed conditions in air atmosphere. The solvent was removed on rotary evaporator after the Schlenk tube was cooled to room temperature. The crude product was purified and separated by column chromatography (eluent ratio: hexane/EtOAc = 60:1) on silica gel to obtain the 1a. Colorless oil (65 mg, 64%), hexane/EtOAc as the eluent (hexane/EtOAc = 60:1, v/v). ¹H NMR (500 MHz, CDCl₃): δ = 8.05 (d, J = 7.8 Hz, 2 H), 7.54 (t, J = 7.4 Hz, 1 H), 7.43 (t, J = 7.6 Hz, 2 H), 6.01 (d, J = 10.1 Hz, 1 H), 5.84 (d, J = 9.0 Hz, 1 H), 5.51 (s, 1 H), 2.14 (dq, J = 18.1, 4.8 Hz, 1 H), 2.09–2.02 (m, 1 H), 1.99–1.94 (m, 1 H), 1.92–1.80 (m, 2 H), 1.74–1.67 (m, 1 H). ¹³C NMR (126 MHz, CDCl₃): δ = 166.39, 132.98, 132.88, 130.94, 129.73, 128.40, 125.88, 68.75, 28.56, 25.10, 19.09.
• 31a Zelentsov SV, Simdyanov IV. Russ. Chem. Bull. 2006; 55: 207
• 31b Font-Sanchis E, Aliaga C, Cornejo R, Scaiano JC. Org. Lett. 2003; 5: 1515
• 32 Chen XY, Yang S, Ren BP, Shi L, Lin DZ, Zhang H, Liu HY. Tetrahedron 2021; 96: 132377
• 33 Mondal R, Chakraborty G, van Vliet KM, van Leest NP, de Bruin B, Paul ND. Inorg. Chim. Acta 2020; 500: 119190
• 34a Conde A, Vilella L, Balcells D, Diaz-Requejo MM, Lledos A, Perez PJ. J. Am. Chem. Soc. 2013; 135: 3887
• 34b Nauert SL, Schax F, Limberg C, Notestein JM. J. Catal. 2016; 341: 180
• 35 Tran BL, Driess M, Hartwig JF. J. Am. Chem. Soc. 2014; 136: 17292
• 36 Romero AH, Sojo F, Arvelo F, Calderon C, Morales A, Lopez SE. Bioorg. Chem. 2020; 101: 104031
• 37 Zhu YF, Wei YY. RSC Adv. 2013; 3: 13668
• 38 Beckwith AL. J, Zavitsas AA. J. Am. Chem. Soc. 1986; 108: 8230
• 39 Rothenberg G, Feldberg L, Wiener H, Sasson Y. J. Chem. Soc., Perkin Trans. 2 1998; 2429