二氧化碳硅氢化及相关转化的均相催化体系研究进展

doi:10.6023/cjoc202306007

摘要/Abstract

利用二氧化碳作为C1原料进行硅氢化转化, 是可持续性催化合成的重要方法之一. 该方法能够将二氧化碳转化为不同氧化水平的高值化学品, 例如甲酸、甲醛、甲醇和甲烷等. 此外, 胺可在特定的催化体系中与二氧化碳和硅烷多组分反应, 实现基于二氧化碳硅氢化的N—H键酰基化和烷基化等转化. 近年来, 二氧化碳硅氢化领域的相关研究取得了显著的进展. 综述了近三年来应用于二氧化碳硅氢化的主要均相催化体系的研究进展, 介绍和总结催化剂的设计和相关催化性能, 包括贵金属催化、廉价过渡金属催化、稀土金属催化、主族金属催化和无金属催化等催化体系, 并讨论和展望了目前二氧化碳硅氢化的研究现状和潜在挑战.

关键词: 二氧化碳, 硅氢化, 均相催化, 碳中和, 可持续性

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

引用此文

苏沛锋, 倪金煜, 柯卓锋. 二氧化碳硅氢化及相关转化的均相催化体系研究进展[J]. 有机化学, 2023, 43(10): 3526-3543.

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.

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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