Oxidative C—H Alkynylation of Unactivated Acyclic Ethers

doi:10.6023/A18030083

Acta Chim. Sinica ›› 2018, Vol. 76 ›› Issue (6): 440-444.DOI: 10.6023/A18030083 Previous Articles Next Articles

Communication

饱和开链醚的氧化碳氢炔基化研究

关弘浩^a, 陈磊^b, 刘磊^a,b

a 山东大学药学院济南 250012;
b 山东大学化学与化工学院济南 250100

投稿日期:2018-03-01 发布日期:2018-05-09
通讯作者: 刘磊,E-mail:leiliu@sdu.edu.cn E-mail:leiliu@sdu.edu.cn
基金资助:
项目受国家自然科学基金（Nos.21722204，21472112）和霍英东青年教师基金（No.151035）资助.

Oxidative C—H Alkynylation of Unactivated Acyclic Ethers

Guan Honghao^a, Chen Lei^b, Liu Lei^a,b

a School of Pharmaceutical Science, Shandong University, Jinan 250012;
b School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100

Received:2018-03-01 Published:2018-05-09
Contact: 10.6023/A18030083 E-mail:leiliu@sdu.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 21722204, 21472112) and Fok Ying Tung Education Foundation (No. 151035).

1. Oxidative C—H Alkynylation of Unactivated Acyclic Ethers.PDF(1701KB)

Abstract

C—C bond forming reactions through cross-dehydrogenative coupling (CDC) of two readily available C—H components under oxidative conditions have emerged as one of the most straightforward and economical approaches for increasing molecular complexity and functional group content with minimal waste generation. CDC reactions involving oxidative functionalization of sp³ C—H bonds of both cyclic and acyclic amines with diverse partners have been extensively explored. In sharp contrast, the CDC of corresponding ether substrates remains relatively underdeveloped. Current approaches predominantly focus on cyclic ethers as well as acyclic benzylic ethers. The CDC reaction of extensively existing unactivated acyclic ethers proved to be much more challenging, which might be ascribed to their inherent low reactivity. On the other hand, the existing protocols for unactivated ethers rely heavily on peroxide-mediated oxidation systems, which typically required high temperature and a large excess of ether substrates as the solvent. Accordingly, coupling partners that can be compatible with such harsh conditions are largely restricted to sp² or sp³ C—H reagents with relatively low manipulation capability, such as arenes, heteroarenes, and 1,3-dicarbonyl moieties. Alkynes represent common structural motifs spread across the fields of biology, chemistry, material science, and medicine, and act as global handles for diverse functionalities. Therefore, the development of a mild approach for CDC of unactivated acyclic ethers with terminal alkynes is highly desired. In 2014, our group developed a mild Ph₃CCl/GaCl₃ mediated oxidation system, allowing to achieve the oxidative C—H alkynylation of tetrahydrofuran with organoboranes. Herein, we reported the first CDC of unactivated acyclic ethers with terminal alkynes promoted by Ph₃CCl/GaCl₃. The reaction proceeded at room temperature in CH₂Cl₂, thus avoiding the employment of excess ether as the solvent. The typical procedure is as follows:a mixture of unactivated acyclic ether (2.0 mmol), terminal alkyne (0.1 mmol), Ph₃CCl (0.1 mmol), and CuI (0.03 mmol) in CH₂Cl₂ at r.t. was added GaCl₃ (0.1 mmol) in a glove box to afford the expected coupling products in moderate to good yields. The Ph₃CCl/GaCl₃ mediated oxidative C—H alkynylation of unactivated acyclic ethers with alkyl substituted alkynylboranes was further established to overcome the relative low efficiency for the CDC reaction involving alkyl substituted terminal alkynes.

Key words: acyclic ether, unactivated ether, terminal alkyne, cross-dehydrogenative coupling, carbocation

Cite this article

Guan Honghao, Chen Lei, Liu Lei. Oxidative C—H Alkynylation of Unactivated Acyclic Ethers[J]. Acta Chim. Sinica, 2018, 76(6): 440-444.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] (a) Godula, K.; Sames, D. Science 2006, 312, 67;
(b) Davies, H. M. L. Angew. Chem., Int. Ed. 2006, 45, 6422;
(c) Gutekunst, W. R.; Baran, P. S. Chem. Soc. Rev. 2011, 40, 1976;
(d) Giri, R.; Shi, B. F.; Engle, K. M.; Maugel, N.; Yu, J. Q. Chem. Soc. Rev. 2009, 38, 3242.
[2] (a) Li, C. J. Acc. Chem. Res. 2009, 42, 335;
(b) Shi, Z.-J. Chin. J. Org. Chem. 2009, 29, 999(in Chinese). (施章杰, 有机化学, 2009, 29, 999.);
(c) Yoo, W. J.; Li, C. J. Top. Curr. Chem. 2010, 292, 281;
(d) Peng, H. M.; Dai, L.-X.; You, S.-L. Angew. Chem., Int. Ed. 2010, 49, 5826;
(e) Scheuermann, C. J. Chem. Asian J. 2010, 5, 436;
(e) Klussmann, M.; Sureshkumar, D. Synthesis 2011, 353;
(f) Yeung, C. S.; Dong, V. M. Chem. Rev. 2011, 111, 1215;
(g) Liu, C.; Zhang, H.; Shi, W.; Lei, A. Chem. Rev. 2011, 111, 1780;
(h) Shi, W.; Liu, C.; Lei, A. Chem. Soc. Rev. 2011, 40, 2761;
(i) Dong, V. M.; Yeung, C. S. Chem. Rev. 2011, 111, 1215;
(j) Zhang, C.; Tang, C.; Jiao, N. Chem. Soc. Rev. 2012, 41, 3464;
(k) Yang, L.; Huang, H. Catal. Sci. Technol. 2012, 2, 1099;
(l) Rohlmann, R.; Garcia Mancheno, O. Synlett 2013, 6;
(m) Qin, Y.; Lv, J.; Luo, S. Tetrhedron Lett. 2014, 55, 551;
(n) Zhang, Y.; Feng, B. Chin. J. Org. Chem. 2014, 34, 2406. (张艳, 冯柏年, 有机化学, 2014, 34, 2406.);
(o) Tan, M.; Gu, Y.; Luo, X.; Zhang, P. Chin. J. Org. Chem. 2015, 35, 781. (谭明雄, 顾运琼, 罗旭健, 张培, 有机化学, 2015, 35, 781.);
(p) Zhong, J.; Meng, Q.; Chen, B.; Tung, C.-H.; Wu, L.-Z. Acta Chim. Sinica 2017, 75, 34(in Chinese). (钟建基, 孟庆元, 陈彬, 佟振合, 吴骊珠, 化学学报, 2017, 75, 34.).
[3] (a) Wender, P. A.; Verma, V. A.; Paxton, T. J.; Pillow, T. H. Acc. Chem. Res. 2008, 41, 40;
(b) Trost, B. M. Acc. Chem. Res. 2002, 35, 695.
[4] For cross-dehydrogenative coupling of amines, see:(a) Li, Z.; Li, C. J. J. Am. Chem. Soc. 2004, 126, 11810;
(b) Li, Z.; Li, C. J. J. Am. Chem. Soc. 2005, 127, 3672;
(c) Li, Z.; Li, C. J. J. Am. Chem. Soc. 2005, 127, 6968;
(d) Li, Z.; Yu, R.; Li, H. Angew. Chem., Int. Ed. 2008, 47, 7497;
(e) Murahashi, S. I.; Nakae, T.; Terai, H.; Komiya, N. J. Am. Chem. Soc. 2008, 130, 11005;
(f) Yang, F.; Li, J.; Xie, J.; Huang, Z.-Z. Org. Lett. 2010, 12, 5214;
(g) Hari, D. P.; Konig, B. Org. Lett. 2011, 13, 3852;
(h) Boess, E.; Sureshkumar, D.; Sud, A.; Wirtz, C.; Fares, C.; Klussmann, M. J. Am. Chem. Soc. 2011, 133, 8106;
(i) Richter, H.; Garcia Mancheno, O. Eur. J. Org. Chem. 2010, 4460;
(j) Meng, Q.-Y.; Zhong, J.-J.; Liu, Q.; Gao, X.-W.; Zhang, H.-H.; Lei, T.; Li, Z.-J.; Feng, K.; Chen, B.; Tung, C.-H.; Wu, L.-Z. J. Am. Chem. Soc. 2013, 135, 19052;
(k) Liu, X.; Sun, B.; Xie, Z.; Qin, X.; Liu, L.; Lou, H. J. Org. Chem. 2013, 78, 3104;
(l) Xie, Z.; Liu, L.; Chen, W.; Zheng, H.; Xu, Q.; Yuan, H.; Lou, H. Angew. Chem., Int. Ed. 2014, 53, 3904;
(m) Wu, C.-J.; Zhong, J.-J.; Meng, Q.-Y.; Lei, T.; Gao, X.-W.; Tung, C.-H.; Wu, L.-Z. Org. Lett. 2015, 17, 884;
(n) Long, H.; Wang, G.; Lu, R.; Xu, M.; Zhang, K.; Qi, S.; He, Y.; Bu, Y.; Liu, L. Org. Lett. 2017, 19, 2146.
[5] For asymmetric cross-dehydrogenative coupling of amines, see:(a) Zhang, J.; Tiwari, B.; Xing, C.; Chen, X.; Chi, Y. R. Angew. Chem., Int. Ed. 2012, 51, 3649;
(b) Zhang, G.; Zhang, Y.; Wang, R.; Angew. Chem., Int. Ed. 2011, 50, 10429;
(c) Zhang, G.; Ma, Y.; Wang, S.; Kong, W.; Wang, R. Chem. Sci. 2013, 4, 2645;
(d) Neel, A. J.; Hehn, J. P.; Tripet, P. F.; Toste, F. D. J. Am. Chem. Soc. 2013, 135, 14044;
(e) Liu, X.; Sun, S.; Meng, Z.; Lou, H.; Liu, L. Org. Lett. 2015, 17, 2396;
(f) Xie, Z.; Liu, X.; Liu, L. Org. Lett. 2016, 18, 2982;
(g) Xie, Z.; Zan, X.; Sun, S.; Pan, X.; Liu, L. Org. Lett. 2016, 18, 3944;
(h) Yang, Q.; Zhang, L.; Ye, C.; Luo, S.; Wu, L.-Z.; Tung, C.-H. Angew. Chem., Int. Ed. 2017, 56, 3694;
(i) Fu, N.; Li, L.; Yang, Q.; Luo, S. Org. Lett. 2017, 19, 2122.
[6] For cross-dehydrogenative coupling of cyclic benzylic ethers, see:(a) Zhang, Y. H.; Li, C. J. J. Am. Chem. Soc. 2006, 128, 4242;
(b) Zhang, Y. H.; Li, C. J. Angew. Chem., Int. Ed. 2006, 45, 1949;
(c) Ghobrial, M.; Harhammer, K.; Mihovilovic, M. D.; Schnürch, M. Chem. Commun. 2010, 46, 8836;
(d) Correia, C. A.; Li, C. J. Heterocycles 2010, 82, 555;
(e) Richter, H.; Rohlmann, R.; Garcia Mancheno, O. Chem. Eur. J. 2011, 17, 11622;
(f) Xiang, S.-K.; Zhang, B.; Zhang, L.-H.; Cui, Y.; Jiao, N. Sci. China Chem. 2012, 55, 50;
(g) Park, S. J.; Price, J. R.; Todd, M. H. J. Org. Chem. 2012, 77, 949;
(h) Liu, X.; Sun, B.; Xie, Z.; Qin, X.; Liu, L.; Lou, H. J. Org. Chem. 2013, 78, 3104;
(i) Chen, W.; Xie, Z.; Zheng, H.; Lou, H.; Liu, L. Org. Lett. 2014, 16, 5988.
[7] Asymmetric cross-dehydrogenative coupling of cyclic benzylic ethers, see:Meng, Z.; Sun, S.; Yuan, H.; Lou, H.; Liu, L. Angew. Chem., Int. Ed. 2014, 53, 543.
[8] For cross-dehydrogenative coupling of unactivated cyclic ethers, see:(a) Wu, Z.; Pi, C.; Cui, X.; Bai, J.; Wu, Y. Adv. Synth. Catal. 2013, 355, 1971;
(b) Huang, X.-F.; Zhu, Z.-Q.; Huang, Z.-Z. Tetrahedron 2013, 69, 8579;
(c) Liu, D.; Liu, C.; Li, H.; Lei, A. Chem. Commun. 2014, 50, 3623;
(d) Wei, W.-T.; Song, R.-J.; Li, J.-H. Adv. Synth. Catal. 2014, 356, 1703;
(e) Jin, J.; MacMillan, D. W. C. Angew. Chem., Int. Ed. 2015, 54, 1565;
(f) Jin, L.; Feng, J.; Lu, G.; Cai, C. Adv. Synth. Catal. 2015, 357, 2105;
(g) Niu, B.; Zhao, W.; Ding, Y.; Bian, Z.; Pittman Jr. C. U.; Zhou, A.; Ge, H. J. Org. Chem. 2015, 80, 7251;
(h) Li, Q.; Hu, W.; Hu, R.; Lu, H.; Li, G. Org. Lett. 2017, 19, 4676;
(i) Liu, S.; Liu, A.; Zhang, Y.; Wang, W. Chem. Sci. 2017, 8, 4044;
(j) Liu, D.; Liu, C.; Lei A. Angew. Chem., Int. Ed. 2013, 52, 4453;
(k) Yang, Q.; Choy, P. Y.; Wu, Y.; Fan, B.; Kwong, F. Y. Org. Biomol. Chem. 2016, 14, 2608;
(l) Zhang, L.; Yi, H.; Wang, J.; Lei, A. J. Org. Chem. 2017, 82, 10704;
(m) Wu, J.; Zhou, Y.; Zhou, Y.; Chiang, C.-W.; Lei, A. ACS Catal. 2017, 7, 8320;
(n) Xie, Z.; Cai, Y.; Hu, H.; Lin, C.; Jiang, J.; Chen, Z.; Wang, L.; Pan, Y. Org. Lett. 2013, 15, 4600;
(o) Zhou, L.; Tang, S.; Qi, X.; Lin, C.; Liu, K.; Liu, C.; Lan, Y.; Lei, A. Org. Lett. 2014, 16, 3404;
(p) Tang, S.; Wang, P.; Li, H.; Lei, A. Nat. Commun. 2016, 7, 11676.
[9] For cross-dehydrogenative coupling of acyclic benzylic ethers, see:(a) Liu, L.; Floreancig, P. E. Org. Lett. 2009, 11, 3152;
(b) Xie, Y.; Yu, M.; Zhang, Y. Synthesis 2011, 17, 2803.
[10] Diederich, F.; Stang, P. J.; Tykwinski, R. R. Acetylene Chemistry:Chemistry, Biology and Material Science, Wiley-VCH, Weinheim, 2005.
[11] Wan, M.; Meng, Z.; Lou, H.; Liu, L. Angew. Chem., Int. Ed. 2014, 53, 13845.
[12] Zhang, Q.; Lv, J.; Luo, S. Acta Chim. Sinica 2016, 74, 61(in Chinese). (张启超, 吕健, 罗三中, 化学学报, 2016, 74, 61.)
[13] Usugi, S.-i.; Yorimitsu, H.; Shinokubo, H.; Oshima, K. Bull. Chem. Soc. Jpn. 2002, 75, 2687.
[14] In-situ generated carbocation oxidation system shows better reactivity than pre-prepared one. At present, the origin of this difference in activity is still unknown.

饱和开链醚的氧化碳氢炔基化研究

Oxidative C—H Alkynylation of Unactivated Acyclic Ethers

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 2

Recommended Articles

Metrics

Comments

[1]	Zhang Qichao, Lü Jian, Luo Sanzhong. Carbocation Lewis Acid Catalyzed Redox-Neutral α-C(sp³)H Arylation of Amines [J]. Acta Chim. Sinica, 2016, 74(1): 61-66.
[2]	LI Jian-Xiao, XUE Fu-Ling, TAN Yue-He, LUO Shi-He, WANG Chao-Yang. Sonogashira Coupling Reaction of 5-Substituted 3,4-Dihalo-2(5H)-furanones [J]. Acta Chimica Sinica, 2011, 69(14): 1688-1696.