Mechanism of Silver-Catalyzed [2+2] Cycloaddition between Siloxy-Alkynes and Carbonyl Compound: A Silylium Ion Migration Approach

doi:10.6023/cjoc202106038

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (11): 4327-4337.DOI: 10.6023/cjoc202106038 Previous Articles Next Articles

ARTICLES

银催化的硅烷氧基炔和羰基化合物的[2+2]环加成机理:硅正离子迁移主导的过程

王恒定^a^,^b, 江凌^a^,^b, 梁鸿雁^c, 樊红军^a^,^b^,^*()

a 中国科学院大连化学物理研究所分子反应动力学国家重点实验室辽宁大连 116023
b 中国科学院大学北京 100864
c 西宁特钢技术中心西宁 810005

收稿日期:2021-06-22 修回日期:2021-08-04 发布日期:2021-08-24
通讯作者: 樊红军
基金资助:
国家重点研发计划(2016YFB0600301); 国家自然科学基金(92061114); 国家自然科学基金(21873096); 中科院战略先导计划(XDB17010200)

Mechanism of Silver-Catalyzed [2+2] Cycloaddition between Siloxy-Alkynes and Carbonyl Compound: A Silylium Ion Migration Approach

Hengding Wang^a^,^b, Ling Jiang^a^,^b, Hongyan Liang^c, Hongjun Fan^a^,^b()

a State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023
b University of Chinese Academy of Sciences, Beijing 100864
c Technical Center, Xining Special Steel Co Ltd., Xining 810005

Received:2021-06-22 Revised:2021-08-04 Published:2021-08-24
Contact: Hongjun Fan
Supported by:
National Key Research and Development Program of China(2016YFB0600301); National Natural Science Foundation of China(92061114); National Natural Science Foundation of China(21873096); Strategic Priority Research Program of Chinese Academy of Sciences(XDB17010200)

1. .pdf(2805KB)

Abstract

Mechanism of silver-catalyzed [2+2] cycloaddition between siloxy-alkynes and α,β-unsaturated carbonyl compound remains controversial. Based on density functional theory (DFT) calculation, it is revealed that Ag⁺ activate siloxy-alkyne into silver-ketene and silylium ion (TIPS⁺) in this reaction. TIPS⁺ then promote [2+2] cycloaddition between α,β-unsaturated carbonyl compound and silver-ketene to form cyclobutane-intermediate, which undergos TIPS⁺ migration and transforms into final product. The mechanism of Ag⁺ catalyzed olefination of aldehydes using siloxy-alkynes was also investigated, the results showed that TIPS⁺ migration also took place in this reaction. In the two reactions studied, Ag⁺ interacts with π-bond of siloxy-alkynes and triggers TIPS⁺ migration, which offers alternative solution to silylium-catalyzed reaction. As similarity of ynolates, silver-ketenes are more stable, which can undergo 1,4-nucleophilic addition with α,β- unsaturated compound. For [2+2] cycloaddition, catalytic variant is rather limited, this work provides a different perspective to obtain four-membered ring products or its ring-open derivates.

Key words: silylium ion, [2+2] cycloaddition, silver-ketene, olefination of aldehyde, siloxy-alkyne

Cite this article

Hengding Wang, Ling Jiang, Hongyan Liang, Hongjun Fan. Mechanism of Silver-Catalyzed [2+2] Cycloaddition between Siloxy-Alkynes and Carbonyl Compound: A Silylium Ion Migration Approach[J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4327-4337.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 9

Scheme 1. Reactions between siloxy-alkynes and carbonyl compound in the presence of π-acid

Scheme 2. Our proposed π-acid and silylium ion exchange mechanism

Figure 1. Free energy profile for TIPSOTf catalyzed [2+2] cycloaddition between siloxy-alkyne 1a and 3-buten-2-one (2a) (a) Free energy profile; (b) Optimized geometries. Gibbs free energies and electronic energy are in kcal/mol. Hydrogen atom was omitted for clarity. Triisopropylsilyl (TIPS) is simplified into big ball except desilication process and versa.

Figure 2. Free energy profile for C—C coupling (a) Free energy profile; (b) Optimized geometries. Gibbs free energies are in kcal/mol. Hydrogen atom was omitted and coordinated ligand was white cloaked for clarity. Triisopropylsilyl (TIPS) is simplified into big ball except desilication process.

Figure 3. Free energy profile for formation final product 3a (a) Free energy profile; (b) Optimized geometries. Gibbs free energies are in kcal/mol. Hydrogen atom was omitted and coordinated ligand was white cloaked for clarity. Triisopropylsilyl (TIPS) is simplified into big ball except desilication process and versa.

Scheme 3. Diastereoselective experiment and deuterium label experiment reported by Kozmin and coworkers

Figure 4. NCI plot of transition states E-A-ts2 and Z-A-ts2 Blue represents strong attraction; green represents van der Waals interaction; red represents strong repulsion or steric effect.

Figure 5. Free energy profiles of olefination of aldehyde using siloxy-alkynes Gibbs free energies are in kcal/mol. Hydrogen atom was omitted and coordinated ligand was white cloaked for clarity. Triisopropylsilyl (TIPS) is simplified into big ball. (a) Free energy profile; (b) Optimized geometries

Scheme 4. Comparation of Ag+ stabilized ynolate anion and Li+ stabilized ynolate anion

References 40

[1]	Hoffmann, R.; Woodward, R. B. Acc. Chem. Res. 1968, 1, 17. doi: 10.1021/ar50001a003
[2]	(a) Xu, C.-H.; Li, Y.; Li, J.-H.; Xiang, J.-N.; Deng, W. Sci. China: Chem. 2019, 62, 1463. doi: 10.1007/s11425-018-9393-6
	(b) Liu, Y.; Bandini, M. Chin. J. Chem. 2019, 37, 431. doi: 10.1002/cjoc.v37.5
	(c) Li, Y.; Jin, G.-F.; An, Y.-Y.; Das, R.; Han, Y.-F. Chin. J. Chem. 2019, 37, 1147. doi: 10.1002/cjoc.v37.11
	(d) Zhang, R.; Yuan, Y.; Qiu, Z.; Xie, Z. Chin. J. Chem. 2018, 36, 273. doi: 10.1002/cjoc.v36.4
	(e) Li, K.; Bai, L.; Luan, X. Chin. J. Org. Chem. 2019, 39, 2211. (in Chinese) doi: 10.6023/cjoc201903065
	(李锟雨, 白璐, 栾新军, 有机化学, 2019, 39, 2211.) doi: 10.6023/cjoc201903065
	(f) Li, Z.; Jian, H.; Wang, W.; Wang, Q.; He, L. Chin. J. Org. Chem. 2018, 38, 2045. (in Chinese) doi: 10.6023/cjoc201802003
	(李志娟, 翦辉, 王伟华, 王强, 何林, 有机化学, 2018, 38, 2045.) doi: 10.6023/cjoc201802003
	(g) Zhao, L.; Tong, X.; Zhu, H.; Yang, D.; Fan, M. Chin. J. Org. Chem. 2017, 37, 646. (in Chinese) doi: 10.6023/cjoc201609014
	(赵立芳, 同晓娟, 祝海涛, 杨得锁, 凡明锦, 有机化学, 2017, 37, 646.) doi: 10.6023/cjoc201609014
[3]	Ohno, H.; Mizutani, T.; Kadoh, Y.; Miyamura, K.; Tanaka, T. Angew. Chem., Int. Ed. 2005, 44, 5113. doi: 10.1002/(ISSN)1521-3773
[4]	Novikov, A. S. Inorg. Chim. Acta 2020, 510, 119758. doi: 10.1016/j.ica.2020.119758
[5]	(a) Arnó, M.; Zaragozá, R. J.; Domingo, L. R. Eur. J. Org. Chem. 2005, 2005, 3973. doi: 10.1002/(ISSN)1099-0690
	(b) Domingo, L. R.; Ríos-Gutiérrez, M.; Silvi, B.; Pérez, P. Eur. J. Org. Chem. 2018, 2018, 1107.
	(c) Mu, B.-S.; Zhang, Z.-H.; Wu, W.-B.; Yu, J.-S.; Zhou, J. Acta Chim. Sinica 2021, 79, 685. (in Chinese) doi: 10.6023/A21040131
	(穆博帅, 张志豪, 武文彪, 余金生, 周剑, 化学学报, 2021, 79, 685.) doi: 10.6023/A21040131
	(d) Lu, P.; Ma, S. Chin. J. Chem. 2010, 28, 1600. doi: 10.1002/cjoc.201090271
[6]	Xu, Y.; Conner, M. L.; Brown, M. K. Angew. Chem., Int. Ed. 2015, 54, 11918. doi: 10.1002/anie.201502815
[7]	(a) Sarkar, D.; Bera, N.; Ghosh, S. Eur. J. Org. Chem. 2020, 2020, 1310. doi: 10.1002/ejoc.201901143 pmid: 27018601
	(b) Poplata, S.; Troster, A.; Zou, Y. Q.; Bach, T. Chem. Rev. 2016, 116, 9748. doi: 10.1021/acs.chemrev.5b00723 pmid: 27018601
	(c) Singh, K.; Trinh, W.; Weaver, J. D. III. Org. Biomol. Chem. 2019, 17, 1854. doi: 10.1039/C8OB01273C pmid: 27018601
	(d) Gan, M.; Zhang, W.; Huo, X.; Han, Y. Sci. Sin.: Chim. 2017, 47, 705. (in Chinese) pmid: 27018601
	(甘明明, 张伟, 霍现宽, 韩英锋, 中国科学: 化学, 2017, 47, 705.) pmid: 27018601
[8]	(a) Ren, X.; Lu, Y.; Lu, G.; Wang, Z. X. Org. Lett. 2020, 22, 2454. doi: 10.1021/acs.orglett.0c00674
	(b) Zhao, L.; Zhang, L.; Fang, D.-C. Organometallics 2016, 35, 3577. doi: 10.1021/acs.organomet.6b00646
	(c) Canellas, S.; Montgomery, J.; Pericas, M. A. J. Am. Chem. Soc. 2018, 140, 17349. doi: 10.1021/jacs.8b09677
	(d) Hoyt, J. M.; Schmidt, V. A.; Tondreau, A. M.; Chirik, P. J. Science 2015, 349, 960. doi: 10.1126/science.aac7440
	(e) Zeng, Z.; Yang, D. Chin. J. Org. Chem. 2013, 33, 2131. (in Chinese) doi: 10.6023/cjoc201301072
	(曾中一, 杨定乔, 有机化学, 2013, 33, 2131.) doi: 10.6023/cjoc201301072
[9]	(a) Boxer, M. B.; Yamamoto, H. Org. Lett. 2005, 7, 3127. doi: 10.1021/ol0512334 pmid: 15771480
	(b) Inanaga, K.; Takasu, K.; Ihara, M. J. Am. Chem. Soc. 2005, 127, 3668. pmid: 15771480
	(c) Shen, L.; Zhao, K.; Doitomi, K.; Ganguly, R.; Li, Y. X.; Shen, Z. L.; Hirao, H.; Loh, T. P. J. Am. Chem. Soc. 2017, 139, 13570. doi: 10.1021/jacs.7b07997 pmid: 15771480
[10]	Takasu, K.; Ueno, M.; Inanaga, K.; Ihara, M. J. Org. Chem. 2004, 69, 517. doi: 10.1021/jo034989u
[11]	(a) Muratore, M. E.; Homs, A.; Obradors, C.; Echavarren, A. M. Chem.-Asian J. 2014, 9, 3066. doi: 10.1002/asia.201402395
	(b) Zhou, L.; Xu, B.; Ji, D.; Zhang, Z.-M.; Zhang, J. Chin. J. Chem. 2020, 38, 577. doi: 10.1002/cjoc.v38.6
	(c) Zhou, Y.; Liu, S.; Chen, H.; Chen, J.; Sun, W.; Li, S.; Yang, Q.; Fan, B. Chin. J. Chem. 2015, 33, 1115. doi: 10.1002/cjoc.201500392
[12]	Sweis, R. F.; Schramm, M. P.; Kozmin, S. A. J. Am. Chem. Soc. 2004, 126, 7442. doi: 10.1021/ja048251l
[13]	Sumaria, C. S.; Turkmen, Y. E.; Rawal, V. H. Org. Lett. 2014, 16, 3236. doi: 10.1021/ol501254h
[14]	Sun, J.; Keller, V. A.; Meyer, S. T.; Kozmin, S. A. Adv. Synth. Catal. 2010, 352, 839. doi: 10.1002/adsc.200900835
[15]	Domingo, L. R.; Ríos-Gutiérrez, M.; Pérez, P. RSC Adv. 2020, 10, 15394. doi: 10.1039/D0RA01548B
[16]	Wang, H.-D.; Fan, H.-J. Commun. Chem. 2020, 3, 126. doi: 10.1038/s42004-020-00373-2
[17]	Turkmen, Y. E.; Montavon, T. J.; Kozmin, S. A.; Rawal, V. H. J. Am. Chem. Soc. 2012, 134, 9062. doi: 10.1021/ja302537j
[18]	Mueller, T. In Functional Molecular Silicon Compounds I: Regular Oxidation States, 155, Eds.: Scheschkewitz, D., Springer, New York, 2014, p. 107.
[19]	Fang, G.; Bi, X. Chem. Soc. Rev. 2015, 44, 8124. doi: 10.1039/C5CS00027K
[20]	Lu, T.; Chen, F. J. Comput. Chem. 2012, 33, 580. doi: 10.1002/jcc.v33.5
[21]	Johnson, E. R.; Keinan, S.; Mori-Sánchez, P.; Contreras-García, J.; Cohen, A. J.; Yang, W. J. Am. Chem. Soc. 2010, 132, 6498. doi: 10.1021/ja100936w pmid: 20394428
[22]	Lu, T.; Chen, Q. Chem. Methods 2021, 1, 231. doi: 10.1002/cmtd.v1.5
[23]	Xiao, P.; Li, C. X.; Fang, W. H.; Cui, G.; Thiel, W. J. Am. Chem. Soc. 2018, 140, 15099. doi: 10.1021/jacs.8b10387 pmid: 30362731
[24]	Domingo, L. R.; Rios-Gutierrez, M.; Perez, P. Molecules 2016, 21, 748. doi: 10.3390/molecules21060748
[25]	Allen, A. D.; Tidwell, T. T. In Advances in Physical Organic Chemistry, Vol. 48, Eds.: Ian, N. H. W.; Williams, H., Elsevier Ltd., UK, 2014, p. 229.
[26]	Antoniotti, S.; Dalla, V.; Dunach, E. Angew. Chem., Int. Ed. 2010, 49, 7860. doi: 10.1002/anie.v49:43
[27]	(a) Kazakova, A. N.; Vasilyev, A. V. Russ. J. Org. Chem. 2017, 53, 485. doi: 10.1134/S1070428017040017
	(b) Greb, L. Chem.-Eur. J. 2018, 24, 17881. doi: 10.1002/chem.v24.68
[28]	(a) Shindo, M.; Matsumoto, K. In Stereoselective Alkene Synthesis, Vol. 327, Ed.: Wang, J., Springer, New York, 2012, p. 1.
	(b) Shindo, M. Synthesis-Stuttgart 2003, 15, 2275.
	(c) Qian, H.; Zhao, W.; Sun, J. Chem. Rec. 2014, 14, 1070. doi: 10.1002/tcr.v14.6
[29]	Allen, A. D.; Tidwell, T. T. ARKIVOC 2016, i, 415.
[30]	Huang, L.; Wu, J.; Hu, J.; Bi, Y.; Huang, D. Tetrahedron Lett. 2020, 61, 151363. doi: 10.1016/j.tetlet.2019.151363
[31]	Lee, V. Y. Russ. Chem. Rev. 2019, 88, 351. doi: 10.1070/RCR4868
[32]	(a) Lambert, J. B.; Zhang, S. H.; Stern, C. L.; Huffman, J. C. Science 1993, 260, 1917. pmid: 21527709
	(b) Kim, K. C.; Reed, C. A.; Elliott, D. W.; Mueller, L. J.; Tham, F.; Lin, L. J.; Lambert, J. B. Science 2002, 297, 825. doi: 10.1126/science.1073540 pmid: 21527709
	(c) Douvris, C.; Ozerov, O. V. Science 2008, 321, 1188. doi: 10.1126/science.1159979 pmid: 21527709
	(d) Allemann, O.; Duttwyler, S.; Romanato, P.; Baldridge, K. K.; Siegel, J. S. Science 2011, 332, 574. doi: 10.1126/science.1202432 pmid: 21527709
[33]	Avcı, Ö. N.; Catak, S.; Dereli, B.; Aviyente, V.; Dedeoglu, B. ChemCatChem 2019, 12, 366. doi: 10.1002/cctc.v12.1
[34]	Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams-Young, D.; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J.,Gaussian 16, Revision C.01, Gaussian, Inc., Wallingford, CT, 2016.
[35]	Chemcraft-graphical software for visualization of quantum chemistry computations. https://www.chemcraftprog.com.
[36]	Chai, J.-D.; Head-Gordon, M. Phys. Chem. Chem. Phys. 2008, 10, 6615. doi: 10.1039/b810189b
[37]	Weigend, F.; Ahlrichs, R. Phys. Chem. Chem. Phys. 2005, 7, 3297. doi: 10.1039/b508541a
[38]	Fukui, K. Acc. Chem. Res. 1981, 14, 363. doi: 10.1021/ar00072a001
[39]	Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378. doi: 10.1021/jp810292n
[40]	(a) Ryu, H.; Park, J.; Kim, H. K.; Park, J. Y.; Kim, S.-T.; Baik, M.-H. Organometallics 2018, 37, 3228. doi: 10.1021/acs.organomet.8b00456
	(b) Wei, C. S.; Jiménez-Hoyos, C. A.; Videa, M. F.; Hartwig, J. F.; Hall, M. B. J. Am. Chem. Soc. 2010, 132, 3078. doi: 10.1021/ja909453g

银催化的硅烷氧基炔和羰基化合物的[2+2]环加成机理:硅正离子迁移主导的过程

Mechanism of Silver-Catalyzed [2+2] Cycloaddition between Siloxy-Alkynes and Carbonyl Compound: A Silylium Ion Migration Approach

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 9

References 40

Related Articles 0

Recommended Articles

Metrics

Comments