Recent Advances in Homogeneous Catalytic Systems for CO2 Hydrosilylation and Related Transformations

doi:10.6023/cjoc202306007

Abstract

Hydrosilylation of carbon dioxide (CO₂) is one of the most significant sustainable approaches for utilizing CO₂ as a C1 feedstock. This approach enables the conversion of CO₂ to value-added chemicals at various oxidation levels, such as formate, formaldehyde, methanol, or methane. Additionally, the formylation and/or alkylation of the N—H bonds of amines can also be achieved in certain catalytic systems with CO₂ and hydrosilanes. Currently, remarkable progress has been made in the field of CO₂ hydrosilylation. This focused review mainly describes advances in the design and catalytic performance of leading catalytic systems reported in the past three years, including noble transition metal catalysis, nonprecious transition metal catalysis, rare-earth metal catalysis, main-group metal catalysis, and metal-free catalysis. Moreover, current bottlenecks and perspectives of this field are also discussed.

Key words: carbon dioxide, hydrosilylation, homogeneous catalysis, carbon neutrality, sustainability

Cite this article

Peifeng Su, Jinyu Ni, Zhuofeng Ke. Recent Advances in Homogeneous Catalytic Systems for CO₂Hydrosilylation and Related Transformations[J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3526-3543.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 25

References 80

[1]	Schuur E. A.; McGuire A. D.; Schadel C.; Grosse G.; Harden J. W.; Hayes D. J.; Hugelius G.; Koven C. D.; Kuhry P.; Lawrence D. M.; Natali S. M.; Olefeldt D.; Romanovsky V. E.; Schaefer K.; Turetsky M. R.; Treat C. C.; Vonk J. E. Nature 2015, 520, 171. doi: 10.1038/nature14338
[2]	Canadell J. G.; Schulze E. D. Nat. Commun. 2014, 5, 5282. doi: 10.1038/ncomms6282 pmid: 25407959
[3]	Hotchkiss J. H.; Werner B. G.; Lee E. Y. C. Compr. Rev. Food Sci. Food Saf. 2006, 5, 158. doi: 10.1111/crfs.2006.5.issue-4
[4]	Cuomo R.; Sarnelli G.; Savarese M. F.; Buyckx M. Nutr. Metab. Cardiovasc. Dis. 2009, 19, 683. doi: 10.1016/j.numecd.2009.03.020 pmid: 19502016
[5]	Singh P.; Wani A. A.; Karim A. A.; Langowski H.-C. Int. J. Dairy Technol. 2012, 65, 161. doi: 10.1111/idt.2012.65.issue-2
[6]	Pearson A. Int. J. Refrig. 2005, 28, 1140. doi: 10.1016/j.ijrefrig.2005.09.005
[7]	Ramsey E.; Sun Q.; Zhang Z.; Zhang C.; Gou W. J. Environ. Sci. 2009, 21, 720. doi: 10.1016/S1001-0742(08)62330-X
[8]	Zhou Y.; Zhu R.; Wei G. Powder Technol. 2021, 389, 21. doi: 10.1016/j.powtec.2021.05.003
[9]	You X.; He S.; Zhang M.; Zeng J.; Li L.; Wang Q.; Wang Q.; Li Y. Steel Res. Int. 2019, 91, 1900450. doi: 10.1002/srin.v91.2
[10]	Maeda C.; Miyazaki Y.; Ema T. Catal. Sci. Technol. 2014, 4, 1482.
[11]	Ye R.-P.; Ding J.; Gong W.; Argyle M. D.; Zhong Q.; Wang Y.; Russell C. K.; Xu Z.; Russell A. G.; Li Q.; Fan M.; Yao Y.-G. Nat. Commun. 2019, 10, 5698. doi: 10.1038/s41467-019-13638-9
[12]	Artz J.; Müller T. E.; Thenert K.; Kleinekorte J.; Meys R.; Sternberg A.; Bardow A.; Leitner W. Chem. Rev. 2017, 118, 434. doi: 10.1021/acs.chemrev.7b00435
[13]	Chauvier C.; Cantat T. ACS Catal. 2017, 7, 2107. doi: 10.1021/acscatal.6b03581
[14]	Kostera S.; Peruzzini M.; Gonsalvi L. Catalysts 2021, 11, 58. doi: 10.3390/catal11010058
[15]	Fernández-Alvarez F. J.; Oro L. A. ChemCatChem 2018, 10, 4783.
[16]	Chen J.; McGraw M.; Chen E. Y. ChemSusChem 2019, 12, 4543. doi: 10.1002/cssc.v12.20
[17]	Wang X.; Xia C.; Wu L. Green Chem. 2018, 20, 5415. doi: 10.1039/C8GC03022G
[18]	Zhang Y.; Zhang T.; Das S. Green Chem. 2020, 22, 1800. doi: 10.1039/C9GC04342J
[19]	Motokura K.; Pramudita R. A. Chem. Rec. 2019, 19, 1199. doi: 10.1002/tcr.201800076
[20]	Fernández-Alvarez F. J.; Aitani A. M.; Oro L. A. Catal. Sci. Technol. 2014, 4, 611. doi: 10.1039/C3CY00948C
[21]	Iglesias M.; Fernández-Alvarez F. J.; Oro L. A. Coord. Chem. Rev. 2019, 386, 240. doi: 10.1016/j.ccr.2019.02.003
[22]	Zhao S.; Liang H.-Q.; Hu X.-M.; Li S.; Daasbjerg K. Angew. Chem., Int. Ed. 2022, 61, e202204008.
[23]	Liu M.; Qin T.; Zhang Q.; Fang C.; Fu Y.; Lin B.-L. Sci. China: Chem. 2015, 58, 1524.
[24]	Li B.; Sortais J.-B.; Darcel C. RSC Adv. 2016, 6, 57603. doi: 10.1039/C6RA10494K
[25]	Liu X.; Li J.; Li N.; Li B.; Bu X.-H. Chin. J. Chem. 2021, 39, 440. doi: 10.1002/cjoc.v39.2
[26]	Jiang Y.; Li G.; Chen Q.; Xu Z.; Lin S.; Guo G. Acta Chim. Sinica 2022, 80, 703 (in Chinese). doi: 10.6023/A22010012
	(蒋银龙, 李国超, 陈青松, 徐忠宁, 林姗姗, 郭国聪, 化学学报, 2022, 80, 703.) doi: 10.6023/A22010012
[27]	Wang X.; Yang X.; Chen C.; Li H.; Huang Y.; Cao R. Acta Chim. Sinica 2022, 80, 22 (in Chinese). doi: 10.6023/A21100455
	(王旭生, 杨胥, 陈春辉, 李红芳, 黄远标, 曹荣, 化学学报, 2022, 80, 22.) doi: 10.6023/A21100455
[28]	Addis D.; Das S.; Junge K.; Beller M. Angew. Chem., Int. Ed. 2011, 50, 6004. doi: 10.1002/anie.v50.27
[29]	Wang H.; Dong Y.; Zheng C.; Sandoval C. A.; Wang X.; Makha M.; Li Y. Chem 2018, 4, 2883. doi: 10.1016/j.chempr.2018.09.009
[30]	Yan F.; Bai J.-F.; Dong Y.; Liu S.; Li C.; Du C.-X.; Li Y. JACS Au 2022, 2, 2522. doi: 10.1021/jacsau.2c00392
[31]	Dong Y.; Yang P.; Zhao S.; Li Y. Nat. Commun. 2020, 11, 4096. doi: 10.1038/s41467-020-17939-2
[32]	Kunihiro K.; Heyte S.; Paul S.; Roisnel T.; Carpentier J. F.; Kirillov E. Chem. Eur. J. 2021, 27, 3997. doi: 10.1002/chem.v27.12
[33]	Guzmán J.; Torguet A.; García-Orduña P.; Lahoz F. J.; Oro L. A.; Fernández-Alvarez F. J. J. Organomet. Chem. 2019, 897, 50. doi: 10.1016/j.jorganchem.2019.06.010
[34]	Guzmán J.; Urriolabeitia A.; Padilla M.; García-Orduña P.; Polo V.; Fernández-Alvarez F. J. Inorg. Chem. 2022, 61, 20216. doi: 10.1021/acs.inorgchem.2c03330
[35]	Guzmán J.; García-Orduña P.; Lahoz F. J.; Fernández-Alvarez F. J. RSC Adv. 2020, 10, 9582. doi: 10.1039/D0RA00204F
[36]	Ojeda-Amador A. I.; Munarriz J.; Alamán-Valtierra P.; Polo V.; Puerta-Oteo R.; Jiménez M. V.; Fernández-Alvarez F. J.; Pérez-Torrente J. J. ChemCatChem 2019, 11, 5524. doi: 10.1002/cctc.201901687
[37]	Roa D. A.; Garcia J. J. New J. Chem. 2023, 47, 4504. doi: 10.1039/D2NJ06204F
[38]	González T.; García J. J. Polyhedron 2021, 203, 115242. doi: 10.1016/j.poly.2021.115242
[39]	Chakraborty S.; Nath R.; Kumar Ray A.; Paul A.; Mandal S. K. Chem. Eur. J. 2022, 28, e202202710.
[40]	Huang Z.; Jiang X.; Zhou S.; Yang P.; Du C.-X.; Li Y. ChemSusChem 2019, 12, 3054. doi: 10.1002/cssc.v12.13
[41]	Bertini F.; Glatz M.; Stöger B.; Peruzzini M.; Veiros L. F.; Kirchner K.; Gonsalvi L. ACS Catal. 2019, 9, 632. doi: 10.1021/acscatal.8b04106
[42]	Buss J. A.; Shida N.; He T.; Agapie T. ACS Catal. 2021, 11, 13294. doi: 10.1021/acscatal.1c02922
[43]	Song Z.; Liu J.; Xing S.; Shao X.; Li J.; Peng J.; Bai Y. Org. Biomol. Chem. 2023, 21, 832. doi: 10.1039/D2OB01986H
[44]	Yang F.; Saiki Y.; Nakaoka K.; Ema T. Adv. Synth. Catal. 2023, 365, 877. doi: 10.1002/adsc.v365.6
[45]	Cramer H. H.; Chatterjee B.; Weyhermuller T.; Werlé C.; Leitner W. Angew. Chem., Int. Ed. 2020, 59, 15674. doi: 10.1002/anie.v59.36
[46]	Cramer H. H.; Ye S.; Neese F.; Werlé C.; Leitner W. JACS Au 2021, 1, 2058. doi: 10.1021/jacsau.1c00350 pmid: 34849511
[47]	Siddique M.; Boity B.; Rit A. Organometallics 2023, 42, 1395. doi: 10.1021/acs.organomet.2c00670
[48]	Li W.-D.; Chen J.; Zhu D.-Y.; Xia J.-B. Chin. J. Chem. 2021, 39, 614. doi: 10.1002/cjoc.v39.3
[49]	Beh D. W.; Piers W. E.; Gelfand B. S.; Lin J.-B. Dalton Trans. 2020, 49, 95. doi: 10.1039/C9DT04323C
[50]	Gurina G. A.; Kissel A. A.; Lyubov D. M.; Luconi L.; Rossin A.; Tuci G.; Cherkasov A. V.; Lyssenko K. A.; Shavyrin A. S.; Ob'edkov A. M.; Giambastiani G.; Trifonov A. A. Dalton Trans. 2020, 49, 638. doi: 10.1039/c9dt04338a pmid: 31819930
[51]	Chang K.; del Rosal I.; Zheng X.; Maron L.; Xu X. Dalton Trans. 2021, 50, 7804. doi: 10.1039/D1DT01074C
[52]	Shinohara K.; Tsurugi H.; Mashima K. ACS Catal. 2022, 12, 8220. doi: 10.1021/acscatal.2c01658
[53]	Zhang Q.; Fukaya N.; Fujitani T.; Choi J.-C. Bull. Chem. Soc. Jpn. 2019, 92, 1945. doi: 10.1246/bcsj.20190203
[54]	Zhang Q.; Lin X.-T.; Fukaya N.; Fujitani T.; Sato K.; Choi J.-C. Green Chem. 2020, 22, 8414. doi: 10.1039/D0GC02890H
[55]	Du C.; Chen Y. Acta Chim. Sinica 2020, 78, 938 (in Chinese). doi: 10.6023/A20060268
	(杜重阳, 陈耀峰. 化学学报, 2020, 78, 938.) doi: 10.6023/A20060268
[56]	Ritter F.; Spaniol T. P.; Douair I.; Maron L.; Okuda J. Angew. Chem., Int. Ed. 2020, 59, 23335. doi: 10.1002/anie.v59.51
[57]	Huang X.; Zhang K.; Shao Y.; Li Y.; Gu F.-L.; Qu L.-B.; Zhao C.; Ke Z. ACS Catal. 2019, 9, 5279. doi: 10.1021/acscatal.9b00879
[58]	Chambenahalli R.; Bhargav R. M.; McCabe K. N.; Andrews A. P.; Ritter F.; Okuda J.; Maron L.; Venugopal A. Chem. Eur. J. 2021, 27, 7391. doi: 10.1002/chem.v27.26
[59]	Ritter F.; Morris L. J.; McCabe K. N.; Spaniol T. P.; Maron L.; Okuda J. Inorg. Chem. 2021, 60, 15583. doi: 10.1021/acs.inorgchem.1c02207
[60]	Ruccolo S.; Amemiya E.; Shlian D. G.; Parkin G. Can. J. Chem. 2021, 99, 259. doi: 10.1139/cjc-2020-0451
[61]	Ruccolo S.; Sambade D.; Shlian D. G.; Amemiya E.; Parkin G. Dalton Trans. 2022, 51, 5868. doi: 10.1039/D1DT04156H
[62]	Sattler W.; Shlian D. G.; Sambade D.; Parkin G. Polyhedron 2020, 187, 114542. doi: 10.1016/j.poly.2020.114542
[63]	Sattler W.; Parkin G. Catal. Sci. Technol. 2014, 4, 1578. doi: 10.1039/c3cy01065a
[64]	Ruccolo S.; Sattler W.; Rong Y.; Parkin G. J. Am. Chem. Soc. 2016, 138, 14542. pmid: 27779860
[65]	Ruccolo S.; Rauch M.; Parkin G. Organometallics 2018, 37, 1708. doi: 10.1021/acs.organomet.8b00158
[66]	Shlian D. G.; Amemiya E.; Parkin G. Chem. Commun. 2022, 58, 4188. doi: 10.1039/D1CC06963B
[67]	Baalbaki H. A.; Shu J.; Nyamayaro K.; Jung H.-J.; Mehrkhodavandi P. Chem. Commun. 2022, 58, 6192. doi: 10.1039/D2CC01498J
[68]	Takaishi K.; Kosugi H.; Nishimura R.; Yamada Y.; Ema T. Chem. Commun. 2021, 57, 8083. doi: 10.1039/D1CC03675K
[69]	Tolzmann M.; Schürmann L.; Hepp A.; Uhl W.; Layh M. Eur. J. Inorg. Chem. 2020, 4024.
[70]	Bolley A.; Specklin D.; Dagorne S. Polyhedron 2021, 194, 114956. doi: 10.1016/j.poly.2020.114956
[71]	Huang W.; Roisnel T.; Dorcet V.; Orione C.; Kirillov E. Organometallics 2020, 39, 698. doi: 10.1021/acs.organomet.9b00853
[72]	Caise A.; Hicks J.; Ángeles Fuentes M.; Goicoechea J. M.; Aldridge S. Chem. Eur. J. 2021, 27, 2138. doi: 10.1002/chem.v27.6
[73]	Rauch M.; Strater Z.; Parkin G. J. Am. Chem. Soc. 2019, 141, 17754. doi: 10.1021/jacs.9b08342
[74]	Sarkar D.; Weetman C.; Dutta S.; Schubert E.; Jandl C.; Koley D.; Inoue S. J. Am. Chem. Soc. 2020, 142, 15403. doi: 10.1021/jacs.0c06287
[75]	Jiang X.; Huang Z.; Makha M.; Du C.-X.; Zhao D.; Wang F.; Li Y. Green Chem. 2020, 22, 5317. doi: 10.1039/D0GC01741H
[76]	Murata T.; Hiyoshi M.; Maekawa S.; Saiki Y.; Ratanasak M.; Hasegawa J.; Ema T. Green Chem. 2022, 24, 2385. doi: 10.1039/D1GC04599G
[77]	Hulla M.; Nussbaum S.; Bonnin A. R.; Dyson P. J. Chem. Commun. 2019, 55, 13089. doi: 10.1039/C9CC06156H
[78]	Murata T.; Hiyoshi M.; Ratanasak M.; Hasegawa J.; Ema T. Chem. Commun. 2020, 56, 5783. doi: 10.1039/D0CC01371D
[79]	Li X.-Y.; Fu H.-C.; Liu X.-F.; Yang S.-H.; Chen K.-H.; He L.-N. Catal. Today 2020, 356, 563. doi: 10.1016/j.cattod.2020.01.030
[80]	Yu Z.; Li Z.; Zhang L.; Zhu K.; Wu H.; Li H.; Yang S. Green Chem. 2021, 23, 5759. doi: 10.1039/D1GC01897C

Entry	Catalyst	Silanes	p(CO₂)/MPa	Other reactant	Solvent	T/℃	t/h	Products
1	1/DCPB^[32]	HSiEt₃	1	C₂H₄	Toluene/H₂O	100	16	Acrylate＋propionate
2	2^[33]	HSiMe₂Ph	0.3	Amine	C₆D₆	50	14	Silylcarbamates
3	3/B(C₆F₅)₃^[34]	HMTS, HSiMe₂Ph, HSiMePh₂, or HSiEt₃	0.1	—	C₆D₆	50	8~40	Bis(silyl)acetals
4	4^[35]	HSiMe(OSiMe₃)₂, HSiMe₂Ph, or HSiMePh₂	0.27	—	C₆D₆	50	3~24	Silylcarbonates＋silylfor- mates＋methoxysilanes
5	5^[36]	HSiMe₂Ph, HSiMePh₂, or HSiEt₃	0.3	—	CD₃CN	75	2~10	Silylformates
6	5^[36]	HSiMe₂Ph	0.3	Amine	CD₃CN	75	15	Silylcarbamates

Entry	Catalyst	Silanes	p(CO₂)/MPa	Other reactant	Solvent	T/℃	t/h	Products
1	1/DCPB^[32]	HSiEt₃	1	C₂H₄	Toluene/H₂O	100	16	Acrylate＋propionate
2	2^[33]	HSiMe₂Ph	0.3	Amine	C₆D₆	50	14	Silylcarbamates
3	3/B(C₆F₅)₃^[34]	HMTS, HSiMe₂Ph, HSiMePh₂, or HSiEt₃	0.1	—	C₆D₆	50	8~40	Bis(silyl)acetals
4	4^[35]	HSiMe(OSiMe₃)₂, HSiMe₂Ph, or HSiMePh₂	0.27	—	C₆D₆	50	3~24	Silylcarbonates＋silylfor- mates＋methoxysilanes
5	5^[36]	HSiMe₂Ph, HSiMePh₂, or HSiEt₃	0.3	—	CD₃CN	75	2~10	Silylformates
6	5^[36]	HSiMe₂Ph	0.3	Amine	CD₃CN	75	15	Silylcarbamates

Entry	Catalyst	Silanes	p(CO₂)/MPa	Other reactants	Solvent	T/℃	t/h	Products
1	6^[37]	H₃SiPh	0.7	—	THF	100	72	Methoxysilanes
2	Mn(CO)₅Br^[38]	HSiEt₃	0.4	—	THF or THF/toluene	50	1	Silylformates＋ bis(silyl)acetals
3^a	7^[39]	H₃SiPh	0.1	Secondary amides or lactams	MeCN	r.t.	12	Acyl formamides
4	8^[40]	H₃SiPh	1.5	Amines	MeCN	r.t.	24	Formamides^b
5	8^[40]	H₃SiPh	0.1	Amines	MeCN	r.t.	24	Formamides
6	8^[40]	H₃SiPh	0.1	Amines	MeCN	100	15	Tertiary amine
7	9^[41]	H₃SiPh	0.1	—	DMSO-d₆	25	1~24	Silylformates＋methoxysilanes
8	9^[41]	H₃SiPh or H₂SiPh₂	0.1	—	DMSO-d₆	80	1~24	Methoxysilanes
9	10^[42]	H₂SiMePh	0.1	—	C₆D₆	70	8	Silanol
10	Cu(OAc)₂/ mPEG-PNP^[43]	HSi(OMe)₃	0.1	Amines	Toluene	30	2	Formamides
11	Cu(OAc)₂^[44]	H₃SiPh	0.1	2-(Methylamino)pyridine	Neat	20	18	Formamides
12^c	12^[45-46]	H₂SiPh₂	0.1	—	Neat	40	4	Silylformates
13^c	12^[45-46]	H₃SiPh	0.1	—	Neat	80	8	Bis(silyl)acetals
14^c	12^[45-46]	H₃SiPh	0.1	—	DMSO-d₆	80	4	Methoxysilanes
15	13^[47]	H₃SiPh	0.1	Anilines	MeCN	r.t.	12	Aryl formamides
16	14/P(n-Bu)₃^[48]	H₃SiPh	0.1	Tryptamine derivative	THF/MeCN (V∶V=1∶1)	60	36	Tertiary amines

Entry	Catalyst	Silanes	p(CO₂)/MPa	Other reactants	Solvent	T/℃	t/h	Products
1	6^[37]	H₃SiPh	0.7	—	THF	100	72	Methoxysilanes
2	Mn(CO)₅Br^[38]	HSiEt₃	0.4	—	THF or THF/toluene	50	1	Silylformates＋ bis(silyl)acetals
3^a	7^[39]	H₃SiPh	0.1	Secondary amides or lactams	MeCN	r.t.	12	Acyl formamides
4	8^[40]	H₃SiPh	1.5	Amines	MeCN	r.t.	24	Formamides^b
5	8^[40]	H₃SiPh	0.1	Amines	MeCN	r.t.	24	Formamides
6	8^[40]	H₃SiPh	0.1	Amines	MeCN	100	15	Tertiary amine
7	9^[41]	H₃SiPh	0.1	—	DMSO-d₆	25	1~24	Silylformates＋methoxysilanes
8	9^[41]	H₃SiPh or H₂SiPh₂	0.1	—	DMSO-d₆	80	1~24	Methoxysilanes
9	10^[42]	H₂SiMePh	0.1	—	C₆D₆	70	8	Silanol
10	Cu(OAc)₂/ mPEG-PNP^[43]	HSi(OMe)₃	0.1	Amines	Toluene	30	2	Formamides
11	Cu(OAc)₂^[44]	H₃SiPh	0.1	2-(Methylamino)pyridine	Neat	20	18	Formamides
12^c	12^[45-46]	H₂SiPh₂	0.1	—	Neat	40	4	Silylformates
13^c	12^[45-46]	H₃SiPh	0.1	—	Neat	80	8	Bis(silyl)acetals
14^c	12^[45-46]	H₃SiPh	0.1	—	DMSO-d₆	80	4	Methoxysilanes
15	13^[47]	H₃SiPh	0.1	Anilines	MeCN	r.t.	12	Aryl formamides
16	14/P(n-Bu)₃^[48]	H₃SiPh	0.1	Tryptamine derivative	THF/MeCN (V∶V=1∶1)	60	36	Tertiary amines

Entry	Catalyst	Silanes	p(CO₂)/MPa	Other reactants	Solvent	T/℃	t/h	Products
1	15/B(C₆F₅)₃^[49]	HSiEt₃	0.1	—	C₆D₆	80	2.5	Bis(silyl)acetals＋ methoxysilanes＋CH₄
2	16/B(C₆F₅)₃^[50]	HSiMe₂Ph, H₃SiPh, or HSiEt₂Me	0.1	—	Toluene	22	4~72	Bis(silyl)acetals＋silo- xanes＋CH₄
3	17/B(C₆F₅)₃^[51]	HSiMePh₂, H₃SiPh, or HSiEt₃	0.5	—	C₆D₆	80	1~13	Bis(silyl)acetals＋silo- xanes＋CH₄
4^a	18/B(3,4,5-F₃C₆H₂)₃^[52]	H₃SiPh	0.1	Anilines	THF	60	4	tertiary amines

二氧化碳硅氢化及相关转化的均相催化体系研究进展

Recent Advances in Homogeneous Catalytic Systems for CO₂Hydrosilylation and Related Transformations

RichHTML

PDF

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 25

References 80

Related Articles 15

Recommended Articles

Metrics

Comments

Entry	Catalyst	Silanes	p(CO₂)/MPa	Other reactants	Solvent	T/℃	t/h	Products
1	Zn(OAc)₂/phen^[53]	H₂SiPh₂	1	—	CD₃CN	r.t.~80	24	Silylformates＋bis(silyl)ace- tals＋methoxysilanes＋CH₄
2	Zn(OAc)₂/phen^[54]	H₃SiPh	0.5	Amines	MeCN	25	4~24	Formamides^a
3	Zn(OAc)₂/phen^[54]	H₂SiPh₂	0.5	Amines	MeCN	120	24	Tertiary amines
4	Zn(OAc)₂/phen^[54]	H₃SiPh	0.5	Amides	MeCN	25~100	24	Acyl formamides
5	Zn(OAc)₂/phen^[54]	H₃SiPh	0.5	Carbamates	MeCN	25~100	24	Formate formamides
6	ZnEt₂^[55]	HSi(OEt)₃	1	—	Neat	90	7	Siloxanes＋methoxysilanes
7	ZnEt₂^[55]	HSi(OEt)₃	1.5	Secondary amines	Neat	100	24	Formamides
8	ZnEt₂^[55]	HSi(OEt)₃	1.5	Primary amines	Neat	100	24	Urea derivatives
9	19^[56]	HSiEtMe₂or HSiⁿBuMe₂	0.1	—	THF	70	8~24	Methoxysilanes＋methyl formate
10^b	20^[58]	H₃SiPh	0.15	—	CD₃CN	60	2	silylformates
11	22^[59]	HSiⁿBuMe₂	0.1	—	THF	70	90	Methoxysilanes＋silylformates
12	23^[59]	HSiⁿBuMe₂	0.1	—	THF	70	90	Methoxysilanes＋silylformates
13	24^[59]	HSiⁿBuMe₂	0.1	—	THF	70	48	Methoxysilanes＋silylformates
14	24^[59]	HSiⁿBuMe₂	0.1	—	THF	70	72	Methoxysilanes
15	25^[59]	HSiⁿBuMe₂	0.1	—	THF	70	48	Silylformates
16	26^[60-61]	HSi[N(CH₂CH₂O)₃] or HSi(OEt)₃	0.1	—	C₆D₆	100	24~264	Methoxysilanes＋silylformates
17	27^[62,66]	HSi(OMe)₃ or HSi(OEt)₃	0.1	—	C₆D₆	r.t.	72	Silylformates
18	28^[67]	HSi(OEt)₃	0.1	—	DMF	60~80	24	Silylformates
19	29^[68]	H₃SiPh	0.1	Anilines or indoles	Neat	60~100	24~96	Anilines or indoles derivatives

Entry	Catalyst	Silanes	p(CO₂)/MPa	Other reactants	Solvent	T/℃	t/h	Products
1	30^[69]	ⁱPr₂Si(H)C≡C^tBu	0.10	—	n-Pentane or n- pentane/n-hexane	r.t.~55	1~12	Silylformates
2	[32][B(C₆F₅)₄]^[70]	HSiEt₃	0.15	—	C₆D₅Br	90	41	Methoxysilanes
3	[33][B(C₆F₅)₄]^[70]	HSiEt₃	0.15	—	C₆D₅Br	90	41	Methoxysilanes
4^a	34^[71]	HSiEt₃	0.60	—	C₆D₅Br or C₆D₆	25~80	5~48	Bis(silyl)acetals＋CH₄
5^a	35^[72]	HSiEt₃	0.20	—	C₆D₆	60	58	Bis(silyl)acetals＋CH₄
6^a	36^[73]	HSiPh₃	0.10	—	C₆H₆	r.t.	672	Bis(silyl)acetals
7	37^[74]	H₂SiPh₂	0.10	Amines	CD₃CN	20~50	2~24	Formamides＋diami- nes＋methyl amines

Entry	Catalyst	Silanes	p(CO₂)/MPa	Other reactants	Solvent	T/℃	t/h	Products
1	38^[75]	H₃SiPh	0.25	Amines	Diglyme	60~100	12	Formamides
2	BPh₃^[76]	H₃SiPh	0.1	Amines	Neat	30~40	6~24	Tertiary amines
3	BPh₃^[76]	H₃SiPh	0.1	Anilines or indoles	Neat	30~40	6~24	Anilines or indoles derivatives
4	39^[77]	H₃SiPh	0.1	Amines	DMSO	23	5	Formamides
5	Cs₂CO₃^[77]	H₃SiPh	0.1	Amines	DMSO	23	5	Formamides
6	TBD^[77]	H₃SiPh	0.1	Amines	DMSO	23	5	Formamides
7	39^[78]	HSiMe₂Ph, HSiMePh₂, HSiPh₃, or H₃SiPh	0.1	—	Neat	30~60	8	Silylformates
8	39^[78]	H₃SiPh or PMHS	0.1	Amines	Neat	30	12	Formamides
9	40^[79]	H₃SiPh	0.5	Amines	Neat	r.t.	12	Formamides
10	41^[80]	H₃SiPh	0.1	Amines	MeCN	25	24	Formamides
11	41^[80]	H₃SiPh	0.1	o-Phenylenediamines	MeCN	25	24	Benzimidazoles
12	41^[80]	H₃SiPh	0.1	o-Hydroxyaniline	MeCN	25	24	Benzoxazole
13	41^[80]	H₃SiPh	0.1	o-Mercaptonoaniline	MeCN	25	24	Benzothiazole

[1]	Xu Liao, Zeyu Wang, Wufei Tang, Jinqing Lin. Progress in Porous Organic Polymer for Chemical Fixation of Carnbon Dioxide [J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2699-2710.
[2]	Zijie Song, Jun Liu, Ying Bai, Jiayun Li, Jiajian Peng. Progress in Catalysis Transformation of Carbon Dioxide through Hydrosilylation [J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2068-2080.
[3]	Shuang Liu, Lianghua Zou, Xiaoming Wang. Advance of Dehydrogenation and Transfer Hydrogenation of Ammonia-Borane Catalyzed by Homogeneous Cobalt Complexes [J]. Chinese Journal of Organic Chemistry, 2023, 43(5): 1713-1725.
[4]	Yongzhou Pan, Xiujin Meng, Yingchun Wang, Muxue He. Recent Progress in Electrochemical Fixation of CO₂ to Construct Carboxylic Acid Derivatives [J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1416-1434.
[5]	Guijie Liu, Zhengqiang Fu, Fei Chen, Caixia Xu, Min Li, Ning Liu. N-Heterocyclic Carbene-Pyridine Manganese Complex/ Tetrabutylammonium Iodide Catalyzed Synthesis of Cyclic Carbonate from CO₂ and Epoxide [J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 629-635.
[6]	Wei Sun, Shoufei Zhu. Hydrosilylation Reactions of Alkene with Tertiary Silanes Catalyzed by Iron-Series Metals [J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3339-3351.
[7]	Xiangqing Feng, Haifeng Du. B(C₆F₅)₃-Catalyzed Silylation of Unsaturated Hydrocarbons [J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3544-3557.
[8]	Fengjuan Chen, Luo Liu, Zilu Zhang, Wei Zeng. Recent Progress in Synthesis of Organosilanes Driven by Visible-Light [J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3454-3469.
[9]	Jun Liu, Jiajian Peng, Ying Bai, Jiayun Li, Zijie Song, Peng Liu, Ting Ouyang, Huilin Lan. Progress in Photocatalytic Hydrosilylation [J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3558-3568.
[10]	Yan Huang, Qian Zhang, Lewu Zhan, Jing Hou, Bindong Li. Hydrocarboxylation of Alkenes with Formate Salts via Photocatalysis [J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2568-2573.
[11]	Yong Xu, Yongxing Zhang, Jia Hu, Cheng Chen, Ye Yuan, Francis Verpoort. Synthesis of β-Oxopropylcarbamates Catalyzed by ZnO/Ionic Liquids under Atmospheric CO₂ [J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2542-2550.
[12]	Fei Chen, Sheng Tao, Ning Liu, Bin Dai. CNN-Type Binuclear Cu(I) Complexes Catalyzed Direct Carboxylation via the Fixation of CO₂ at Room Temperature [J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2471-2480.
[13]	Youcai Zhu, Xinxin Ding, Li Sun, Zhen Liu. Advances in the Production of Acrylic Acid and Its Derivatives by CO₂/C₂H₄ Coupling [J]. Chinese Journal of Organic Chemistry, 2022, 42(4): 965-977.
[14]	Xin Li, Qiuling Song. Chiral Borane-Catalyzed Enantioselective Reactions [J]. Chinese Journal of Organic Chemistry, 2022, 42(10): 3143-3151.
[15]	Peng Wang, Da Yang, Huan Liu. Recent Advances on Carbonylation of 1,3-Dienes [J]. Chinese Journal of Organic Chemistry, 2021, 41(9): 3379-3389.