无过渡金属参与的碳硅键构筑方法研究进展

doi:10.6023/cjoc202307017

摘要/Abstract

有机硅化合物在合成、制药和检测等许多领域有着广泛的应用. 鉴于其重要性, 有机硅化合物的合成方法学研究颇受关注. 其中, 在成本和环境友好性等方面的突出优势, 无过渡金属参与的碳硅键构筑作为过渡金属催化偶联策略的主要替代方法, 在过去几年中得到了发展并被应用于多种有机硅化合物的合成中. 以反应催化剂(引发剂)的种类为框架, 进一步按照反应中形成的碳硅键类型分类, 总结了近期发表的无过渡金属参与碳硅键构建方法, 对部分代表性的反应机理做了简要说明, 并对未来发展方向提出简要展望.

关键词: 无过渡金属, 碳硅键构筑, 有机硅, 绿色化学

Organosilicons are widely used in many chemistry related fields. Given its important role, the chemical syntheses of organosilicon compounds have received considerable attention. Due to outstanding advantages in cost and environmental friendliness, transition-metal-free C—Si bond formation has been widely studied in the past decades and has been emerged as an important alternative to transition-metal-catalyzed C—Si cross-coupling. In this review, the recent developed methods of carbon-silicon bond formation under transition-metal-free conditions are summarized. The discussion is organized according to catalysts (acid catalysis, base catalysis, and radical initiation) and the types of C—Si bonds that formed. In addition, mechanistic discussions of representative reactions and a prospect for future development in this field are also briefly included.

Key words: transition-metal-free, C—Si bond formation, organosilicons, green chemistry

引用此文

李奇阳, 张海燕, 刘文博. 无过渡金属参与的碳硅键构筑方法研究进展[J]. 有机化学, 2023, 43(10): 3470-3490.

Qiyang Li, Haiyan Zhang, Wenbo Liu. Research Progress in Transition-Metal-Free C—Si Bond Formation[J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3470-3490.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 39

图式1. 路易斯酸催化的还原硅化反应一般机理

Scheme 1. General mechanism of Lewis acid-catalyzed reductive silylation reaction

图式2. 喹啉的β位硅基化还原反应

Scheme 2. β-Silylative reduction of quinolines

图式3. 吡啶的选择性还原硅化反应

Scheme 3. Selective silylative reduction of pyridines

图式4. 呋喃的连续开环-闭环反应

Scheme 4. Ring-opening and closing cascades of furans

图式5. 丙烯腈与不饱和亚胺的还原硅化

Scheme 5. Silylative reductive of conjugated nitriles and unsaturated imines

图式6. 磷(III) Lewis酸介导的烯烃氢硅基化反应

Scheme 6. Olefin hydrosilylation mediated by phosphorus(III) Lewis acid

图式7. 苄基取代的乙烯基环丙烷的硅基化

Scheme 7. Silylation of the benzyl-substituted vinylcyclopropanes

图式8. 叔胺的连续硅基化反应

Scheme 8. Consecutive silylation of tertiary amines

图式9. 芳香胺的碳氢键硅基化反应

Scheme 9. C—H bond silylation of aromatic amine

图式10. 吲哚的汇聚歧化反应

Scheme 10. Convergent disproportionation reaction of indoles

图式11. 吲哚的汇聚歧化反应机理

Scheme 11. Mechanism of convergent disproportionation reaction of indoles

图式12. Al(C6F5)3催化的C—H硅基化

Scheme 12. C—H silylation of indoles catalyzed by Al(C6F5)3

图式13. 哌啶的串联硅基化反应

Scheme 13. Cascade silylation of piperidines

图式14. 端炔C—H硅基化反应

Scheme 14. C—H silylation of terminal alkynes

图式15. (杂)芳烃的C—H脱质子硅基化反应

Scheme 15. Deprotonative C—H silylation of (hetero-)arenes

图式16. 叔丁醇钾催化的杂芳烃脱氢硅化反应

Scheme 16. tBuOK-catalyzed dehydrogenative silylation of heteroaromatics

图式17. 杂芳烃脱氢硅化反应机理

Scheme 17. Mechanism of dehydrogenative silylation of heteroaromatics

图式18. 氮杂环选择性C(sp2)—H硅基化反应

Scheme 18. Site-selective C(sp2)—H silylation of azines

图式19. 碱金属氢氧化物催化的C(sp)—H硅基化反应

Scheme 19. Alkali metal-hydroxide-catalyzed C(sp)—H silylation

图式20. DMPU介导的苯乙炔类化合物硅烷化反应

Scheme 20. DMPU-mediated silylation of substituted phenylacetylene

图式21. 硅基二氮烯在C(sp2)—H键硅基化反应中的应用

Scheme 21. Application of silyldiazenes in silylation of C(sp2)—H bond

图式22. α-氧代频哪醇硼烷在叔丁醇钠作用下的偕二硅硼化反应

Scheme 22. tBuONa-mediated gem-silylborylation of α-oxyboronates

图式23. 铵盐在碱作用下的硼硅化/硅化取代反应

Scheme 23. Base-mediated borylsilylation/silylation of ammonium salts

图式24. 氟代烃的协同脱氟硅化取代反应

Scheme 24. Silyldefluorination of fluorohydrocarbon by concerted substitution

图式25. 氟代芳烃的协同脱氟硅化取代反应

Scheme 25. Silyldefluorination of fluoroarenes by concerted substitutioni

图式26. 叔丁醇钾催化的氮杂芳烃的1,2-硅硼化

Scheme 26. KOtBu-catalyzed 1,2-silaboration of N-heteroarenes

图式27. 对亚甲基苯醌的硅基化-芳构化反应

Scheme 27. Silylative aromatization of p-quinone methides

图式28. 吲哚/苯并呋喃的开环硅化反应

Scheme 28. Ring-opening silylation of indoles and benzofurans

图式29. 氟化铯参与的苯乙烯进行反马氏氢三甲硅基化加成

Scheme 29. CsF-mediated hydrotrimethylsilylation of styrenes with anti-Markovnikov selectivity

图式30. 氮杂芳烃的自由基硅基化反应

Scheme 30. Radical silylation of electron-deficient N-hetero- arenes

图式31. 烯基酰胺的脱氢硅化反应

Scheme 31. Dehydrogenative silylation of enamides

图式32. 碱促进的均裂型芳香取代(BHAS)合成9-硅芴

Scheme 32. Synthesis of 9-silafluorenes via base-promoted homolytic aromatic substitution (BHAS)

图式33. 自由基介导的芳基烯基硫醚断裂C—S键合成乙烯基硅烷

Scheme 33. Radical-mediated synthesis of alkenyl silanes by C—S bond cleavage of arylalkenyl sulfides

图式34. 自由基氧化反应制备含硅杂环化合物

Scheme 34. Oxidative radical reaction access to Si-containing heterocycles

图式35. 自由基引发的级联加成-环化反应

Scheme 35. Radical-initiated cascade addition/cyclization

图式36. 钙单质还原断裂C—O键启动的区域选择性硅基化

Scheme 36. Regioselective silylations through Ca-promoted reductive C—O bond cleavage

图式37. 乙烯基芳烃的氢原子转移(HAT)氢硅化反应

Scheme 37. Hydrogen atom transfer(HAT) to vinylarenes for hydrosilylation

图式38. 钙催化(杂)芳基化合物的脱氢硅基化反应

Scheme 38. Calcium-catalyzed dehydrogenative silylation of (hetero-)arenes

图式39. 有机钙螯合物催化的碳硅键构筑方法

Scheme 39. Organocalcium complex-catalyzed C—Si bond formation

参考文献 77

[1]	Brook M. A. Silicon in Organic, Organometallic, and Polymer Chemistry, Wiley, New York, 2000.
[2]	Franz A. K.; Wilson S. O. J. Med. Chem. 2013, 56, 388. doi: 10.1021/jm3010114
[3]	(a) Feng S.-Y.; Qu Z.-R.; Zhou Z.-K.; Chen J.-Y.; Gai L.-Z.; Lu H.; Chem. Commun. 2021, 57, 11689. doi: 10.1039/D1CC04687J
	(b) Salgues B.; Sarkar R.; Fajri M. L.; Avalos-Quiroz Y. A.; Manick A.; Giorgi M.; Vanthuyne N.; Carissan Y.; Videlot- Ackermann C.; Ackermann J.; Canard G.; Parrain J.; Guennic B. L.; Jacquemin D.; Amatore M.; Commeiras L.; Zaborova E.; Fages F. J. Org. Chem. 2022, 87, 3276. doi: 10.1021/acs.joc.1c02942
[4]	(a) Poole C. F. J. Chromatogr. A 2013, 1296, 2. doi: 10.1016/j.chroma.2013.01.097
	(b) Hsieh C.-Z.; Chung W.-H.; Ding W.-H. RSC Adv. 2021, 11, 23607. doi: 10.1039/D1RA04195A
[5]	(a) Metsänen T. T.; Gallego D.; Szilvási T.; Driess M.; Oestreich M. Chem. Sci. 2015, 6, 7143. doi: 10.1039/c5sc02855h pmid: 27136183
	(b) Bleith T.; Gade L. H. J. Am. Chem. Soc. 2016, 138, 6074. doi: 10.1021/jacs.6b03576 pmid: 27136183
	(c) Park S.; Chang S. Angew. Chem., Int. Ed. 2017, 56, 7720. doi: 10.1002/anie.v56.27 pmid: 27136183
[6]	Muramatsu W.; Yamamoto H. J. Am. Chem. Soc. 2021, 143, 6792. doi: 10.1021/jacs.1c02600
[7]	Bellan A. B.; Knochel P. Angew. Chem., Int. Ed. 2019, 58, 1838. doi: 10.1002/anie.v58.6
[8]	McWilliams S. F.; Broere D. L. J.; Halliday C. J. V.; Bhutto S. M.; Mercado B. Q.; Holland P. L. Nature 2020, 584, 221. doi: 10.1038/s41586-020-2565-5
[9]	(a) Verma V.; Koperniku A.; Edwards P. M.; Schafer L. L. Chem. Commun. 2022, 58, 9174. doi: 10.1039/D2CC02915D pmid: 33356223
	(b) Kuci'nski K.; Stachowiak H.; Lewandowski D.; Gruszczy'nski M.; Lampasiak P.; Hreczycho G. J. Organomet. Chem. 2022, 961, 122127. doi: 10.1016/j.jorganchem.2021.122127 pmid: 33356223
	(c) Matsuoka K.; Komami N.; Kojima M.; Mita T.; Suzuki K.; Maeda S.; Yoshino T.; Matsunaga S. J. Am. Chem. Soc. 2021, 143, 103. doi: 10.1021/jacs.0c11645 pmid: 33356223
[10]	(a) Langkopf E.; Schinzer D. Chem. Rev. 1995, 95, 1375. doi: 10.1021/cr00037a011 pmid: 29938502
	(b) Chatgilialoglu C.; Ferreri C.; Landais Y.; Timokhin V. I. Chem. Rev. 2018, 118, 6516. doi: 10.1021/acs.chemrev.8b00109 pmid: 29938502
[11]	Littleson M. M.; Campbell A. D.; Clarke A.; Dow M.; Ensor G.; Evans M. C.; Herring A.; Jackson B. A.; Jackson L. V.; Karlsson S.; Klauber D. J.; Legg D. H.; Leslie K. W.; Moravčík Š.; Parsons C. D.; Ronson T. O.; Meadows R. E. Org. Process Res. Dev. 2019, 23, 1407. doi: 10.1021/acs.oprd.9b00171
[12]	Komiyama T.; Minami Y.; Hiyama T. ACS Catal. 2017, 7, 631. doi: 10.1021/acscatal.6b02374
[13]	(a) Yang Y.-H.; Wang C.-Y. Sci. China Chem. 2015, 58, 1266. doi: 10.1007/s11426-015-5375-0
	(b) Lipke M. C.; Liberman-Martin A. L.; Tilley T. D. Angew. Chem., Int. Ed. 2017, 56, 2260. doi: 10.1002/anie.v56.9
[14]	Schuman D. P.; Liu W.-B.; Nesnas N.; Stoltz B. M. Organosilicon Chemistry: Novel Approaches and Reactions, Eds.: Hiyama, T.; Oestreich, M., Wiley-VCH Verlag GmbH & Co. KGaA, New York, 2019.
[15]	Tyagi A.; Yadav N.; Khan J.; Singh S.; Hazra C. K. Asian J. Org. Chem. 2021, 10, 334. doi: 10.1002/ajoc.v10.2
[16]	Bähr S.; Oestreich M. Angew. Chem., Int. Ed. 2017, 56, 52. doi: 10.1002/anie.v56.1
[17]	Gandhamsetty N.; Joung S.; Park S.-W.; Park S.; Chang S. J. Am. Chem. Soc. 2014, 136, 16780. doi: 10.1021/ja510674u pmid: 25412033
[18]	Gandhamsetty N.; Park S.; Chang S. J. Am. Chem. Soc. 2015, 137, 15176. doi: 10.1021/jacs.5b09209 pmid: 26580152
[19]	Hazra C. K.; Gandhamsetty N.; Park S.; Chang S. Nat. Commun. 2016, 7, 13431. doi: 10.1038/ncomms13431
[20]	Gandhamsetty N. Park J.; Jeong J.; Park S.-W.; Park S.; Chang S. Angew. Chem., Int. Ed. 2015, 54, 6832. doi: 10.1002/anie.v54.23
[21]	Kim E.; Park S.; Chang S. Chem. Eur. J. 2018, 24, 5765. doi: 10.1002/chem.v24.22
[22]	Pérez M.; Hounjet L.; Caputo C.; Dobrovetsky R.; Stephan D. J. Am. Chem. Soc. 2013, 135, 18308. doi: 10.1021/ja410379x
[23]	Andrews R.; Chitnis S.; Stephan D. Chem. Commun. 2019, 55, 5599 doi: 10.1039/C9CC02460C
[24]	Parks D.; Blackwell J.; Piers W. J. Org. Chem. 2000, 65, 3090 doi: 10.1021/jo991828a pmid: 10814201
[25]	He T.; W, G.-Q.; Long P.-W.; Kemper S.; Irran E.; Klare H. F. T.; Oestreich M. Chem. Sci. 2021, 12, 569. doi: 10.1039/D0SC05553K
[26]	Fang H.-Q.; Xie K.X.; Kemper S.; Oestreich M. Angew. Chem., Int. Ed. 2021, 60, 8542. doi: 10.1002/anie.v60.15
[27]	Ma Y.-H.; Wang B.-L.; Zhang L.; Hou Z.-M. J. Am. Chem. Soc. 2016, 138, 3663. doi: 10.1021/jacs.6b01349
[28]	Han Y.-X.; Zhang S.-T.; He J.-H.; Zhang Y.-T. J. Am. Chem. Soc. 2017, 139, 7399. doi: 10.1021/jacs.7b03534
[29]	Han Y.-X.; Zhang S.; He J.-H.; Zhang Y.-T. ACS Catal. 2018, 8, 8765. doi: 10.1021/acscatal.8b01847
[30]	Zhang J.-B.; Park S.; Chang S. J. Am. Chem. Soc. 2018, 140, 13209. doi: 10.1021/jacs.8b08733
[31]	Ma Y.-H.; Lou S.-J.; Luo G.; Luo Y.; Zhan G.; Nishiura M.; Luo Y.; Hou Z.-M. Angew. Chem., Int. Ed. 2018, 57, 15222. doi: 10.1002/anie.v57.46
[32]	Sasaki M.; Kondo Y. Org. Lett. 2015, 17, 848. doi: 10.1021/ol503671b
[33]	Toutov A.; Liu W.-B.; Betz K. N.; Fedorov A.; Stoltz B. M.; Grubbs R. H. Nature 2015, 518, 80. doi: 10.1038/nature14126
[34]	Banerjee S.; Yang Y.-F.; Jenkins I. D.; Liang Y.; Toutov A. A.; Liu W.-B.; Schuman D. P.; Grubbs R. H.; Stoltz B. M.; Krenske E. H.; Houk K. N.; Zare R. N. J. Am. Chem. Soc. 2017, 139, 6880. doi: 10.1021/jacs.6b13032 pmid: 28462580
[35]	Liu W.-B.; Schuman D. P.; Yang Y.-F.; Toutov A. A.; Liang Y.; Klare H. F. T.; Nesnas N.; Oestreich M.; Blackmond D. G.; Virgil S. C.; Banerjee S.; Zare R. N.; Grubbs R. H.; Houk K. N.; Stoltz B. M. J. Am. Chem. Soc. 2017, 139, 6867. doi: 10.1021/jacs.6b13031
[36]	Gu Y.-T.; Shen Y.-Y.; Zarate C.; Martin R. J. Am. Chem. Soc. 2019, 141, 127. doi: 10.1021/jacs.8b12063
[37]	Toutov A. A.; Betz K. N.; Schuman D. P.; Liu W.-B.; Fedorov A.; Stoltz B. M.; Grubbs R. H. J. Am. Chem. Soc. 2017, 139, 1668. doi: 10.1021/jacs.6b12114 pmid: 28026952
[38]	Nozawa-Kumada K.; Inagi M.; Kondo Y. Asian J. Org. Chem. 2017, 6, 63. doi: 10.1002/ajoc.v6.1
[39]	Neil B.; Lucien F.; Fensterbank L.; Chauvier C. ACS Catal. 2021, 11, 13085. doi: 10.1021/acscatal.1c03824
[40]	Wang L.; Zhang T.; Sun W.; He Z.-Y.; Xia C.-G.; Lan Y.; Liu C. J. Am. Chem. Soc. 2017, 139, 5257. doi: 10.1021/jacs.7b02518 pmid: 28306251
[41]	Qi W.-Y.; Zhen J.-S.; Xu X.-H.; Du X.; Li Y.-H.; Yuan H.; Guan Y.-S.; We X.; Wang Z.-Y.; Liang G.-H.; Luo Y. Org. Lett. 2021, 23, 5988. doi: 10.1021/acs.orglett.1c02066
[42]	Liu X.-W.; Zarate C.; Martin R. Angew. Chem., Int. Ed. 2019, 58, 2064. doi: 10.1002/anie.v58.7
[43]	Mallick S.; Xu P.; Wgrthwein E.; Studer A. Angew. Chem., Int. Ed. 2019, 58, 283. doi: 10.1002/anie.v58.1
[44]	Oestreich M.; Hartmann E.; Mewald M. Chem. Rev. 2013, 113, 402. doi: 10.1021/cr3003517 pmid: 23163551
[45]	Ito H.; Horit Y.; Yamamoto E. Chem. Commun. 2012, 48, 8006. doi: 10.1039/c2cc32778c
[46]	Morimasa Y.; Kabasawa K.; Ohmura T.; Suginome M. Asian J. Org. Chem. 2019, 8, 1092. doi: 10.1002/ajoc.201900176
[47]	Nagao K.; Ohmiya H.; Sawamura M. Org. Lett. 2015, 17, 1304. doi: 10.1021/acs.orglett.5b00305
[48]	Gu Y.-T.; Duan Y.-Y.; Shen Y.-Y.; Martin R. Angew. Chem., Int. Ed. 2020, 59, 2061. doi: 10.1002/anie.v59.5
[49]	Jeong E.; Heo J.; Jin S.; Kim D.; Chang S. ACS Catal. 2022, 12, 4898. doi: 10.1021/acscatal.2c01126
[50]	Huo Y.-W.; Shen P.-P.; Duan W.-Z.; Zhen C.; Song C.; Ma Y.-D. Chin. Chem. Lett. 2018, 29, 1359. doi: 10.1016/j.cclet.2017.12.005
[51]	Li T.-T.; Wu Y.-Z.; Duan W.-Z.; Ma Y.-D. RSC Adv. 2021, 11, 17860. doi: 10.1039/D1RA03193G
[52]	Xu P.; Würthwein E.; Daniliuc C.; Studer A. Angew. Chem., Int. Ed. 2017, 56, 13872. doi: 10.1002/anie.v56.44
[53]	Wang X.; Yu Z.-X.; Liu W.-B. Org. Lett. 2022, 24, 8735. doi: 10.1021/acs.orglett.2c03170
[54]	Shang X.-J.; Liu Z.-Q. Org. Biomol. Chem. 2016, 14, 7829. doi: 10.1039/C6OB00797J
[55]	Chatgilialoglu C.; Ferreri C.; Landais Y.; Timokhin V. I. Chem. Rev. 2018, 118, 6516. doi: 10.1021/acs.chemrev.8b00109 pmid: 29938502
[56]	Zhang X.-P.; Fang J.-K.; Cai C.; Lu G.-P. Chin. Chem. Lett. 2021, 32, 1280. doi: 10.1016/j.cclet.2020.09.058
[57]	Li J.-S.; Wu J. ChemPhotoChem 2018, 2, 839. doi: 10.1002/cptc.v2.10
[58]	Ren L.-Q.; Li N.; Ke J.; He C. Org. Chem. Front. 2022, 9, 6400. doi: 10.1039/D2QO01387H
[59]	Sakamoto R.; Nguyen B.; Maruoka K. Asian J. Org. Chem. 2018, 7, 1085. doi: 10.1002/ajoc.v7.6
[60]	Chang X.-H.; Wang Z.-L.; Zhao M.; Yang C.; Li J.-J.; Ma W.-W.; Xu Y.-H. Org. Lett. 2020, 22, 1326. doi: 10.1021/acs.orglett.9b04645
[61]	Leifert D.; Studer A. Org. Lett. 2015, 17, 386. doi: 10.1021/ol503574k pmid: 25536028
[62]	Studer A.; Curran D. P. Nat. Chem. 2014, 6, 765. doi: 10.1038/nchem.2031
[63]	Lin Y.-M.; Lu G.-P.; Wang R.-K.; Yi W.-B. Org. Lett. 2017, 19, 1100. doi: 10.1021/acs.orglett.7b00126
[64]	Yang Y.; Song R.-J.; Li Y.; Ouyang X.-H.; Li J.-H.; He D.-L. Chem. Commun. 2018, 54, 1441. doi: 10.1039/C7CC08964C
[65]	Zhang C.; Pi J.-X.; Wang L.; Liu P.; Sun P.-P. Org. Biomol. Chem. 2018, 16, 9223. doi: 10.1039/c8ob02670j pmid: 30475364
[66]	Zhang T.-Y.; Zheng S.-H.; Kobayashi T.; Maekawa H. Org. Lett. 2021, 23, 7129. doi: 10.1021/acs.orglett.1c02532
[67]	Asgari P.; Hua Y.-D.; Bokka A.; Thiamsiri C.; Prasitwatcharakorn W.; Karedath A.; Chen X.; Sardar S.; Yum K.; Leem G.; Pierce B. S.; Nam K.; Gao J.-L.; Jeon J. Nat. Catal. 2019, 2, 164. doi: 10.1038/s41929-018-0217-z
[68]	Buch F.; Brettar J.; Harder S. Angew. Chem., Int. Ed. 2006, 45, 2741. doi: 10.1002/anie.v45:17
[69]	Leich V.; Spaniol T.; Maron L.; Okuda J. Chem. Commun. 2014, 50, 2311 doi: 10.1039/c3cc49308c
[70]	Schuhknecht D.; Spaniol T.; Maron L.; Okuda J. Angew. Chem., Int. Ed. 2020, 59, 310. doi: 10.1002/anie.v59.1
[71]	Liu Z.-Z.; Shi X.-H.; Cheng J.-H. Dalton Trans. 2020, 49, 8340. doi: 10.1039/D0DT01158D
[72]	Zhao L.-X.; Shi X.-H.; Cheng J.-H. ACS Catal. 2021, 11, 2041. doi: 10.1021/acscatal.0c05440
[73]	Gong X.; Deng P.; Cheng J.-H. ChemCatChem 2022, 14, e202200060.
[74]	Li T.; McCabe K. N.; Maron L.; Leng X.-B.; Chen Y.-F. ACS Catal. 2021, 11, 6348. doi: 10.1021/acscatal.1c00463
[75]	Liu R.-X.; Liu X.-J.; Cheng T.-Y.; Chen Y.-F. Eur. J. Org. Chem. 2022, 1, e202101218.
[76]	Li T.; Liu R.-X.; Liu X.-J.; Chen Y.-F. Org. Lett. 2023, 25, 761 doi: 10.1021/acs.orglett.2c04230
[77]	Wang L.-L.; Li Y.-H.; Li Z.-F.; Kira M. Coord. Chem. Rev. 2022, 457, 214413. doi: 10.1016/j.ccr.2022.214413