新型含酯基官能团的茂基金属铑催化剂的合成及其在催化合成异喹啉反应中的应用

doi:10.6023/cjoc202402014

摘要/Abstract

在茂基上引入一个酯基官能团, 合成了一类新型的茂基金属铑催化剂. 此催化剂被应用于催化芳基肟与炔的碳氢活化[4＋2]环加成合成四氢异喹啉的反应中. 结果表明, 该催化剂在反应活性以及醋酸盐用量方面都优越于常规催化剂[Cp*RhCl₂]₂.

关键词: 异喹啉, 茂基金属铑络合物, [4＋2]环加成反应, 肟, 炔

A new type of cyclopentadienyl metal rhodium catalyst was synthesized by introducing an ester functional group onto the cyclopentadienyl group. The catalyst was evaluated with C—H active [4＋2] annulation of aryl oximes and alkynes. The result demonstrated that the new catalyst was superior to conventional catalysts [Cp*RhCl₂]₂ in terms of reactivity and the usage of the metal acetate added.

Key words: iso-quinoline, Rh-Cp complex, [4＋2] annulation, oxime, alkyne

引用此文

金欢, 朱彦军, 李芳, 罗云飞. 新型含酯基官能团的茂基金属铑催化剂的合成及其在催化合成异喹啉反应中的应用[J]. 有机化学, 2024, 44(9): 2906-2914.

Huan Jin, Yanjun Zhu, Fang Li, Yunfei Luo. Synthesis of New Rh-Cp Complex with an Ester Group Tethered on the Cp Ring and Its Application in the Catalytic Synthesis of iso-Quinolines[J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2906-2914.

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Entry	Solvent	Additive	Yield^b/%
1	CH₃OH	Cu(OAc)₂	95
2^c	CH₃OH	Cu(OAc)₂	NR
3	Toluene	Cu(OAc)₂	NR
4	Acetone	Cu(OAc)₂	14
5	DMF	Cu(OAc)₂	10
6	CH₃CN	Cu(OAc)₂	NR
7	THF	Cu(OAc)₂	NR
8	CH₃CH₂OH	Cu(OAc)₂	17
9	CH₃OH	Zn(OAc)₂	23
10	CH₃OH	AgOAc	78
11	CH₃OH	NaOAc	24
12	CH₃OH	KOAc	31
13^d	CH₃OH	Cu(OAc)₂	80
14^e	CH₃OH	Cu(OAc)₂	34
15	CH₃OH	—	30
16^f	CH₃OH	—	NR

Entry	Solvent	Additive	Yield^b/%
1	CH₃OH	Cu(OAc)₂	95
2^c	CH₃OH	Cu(OAc)₂	NR
3	Toluene	Cu(OAc)₂	NR
4	Acetone	Cu(OAc)₂	14
5	DMF	Cu(OAc)₂	10
6	CH₃CN	Cu(OAc)₂	NR
7	THF	Cu(OAc)₂	NR
8	CH₃CH₂OH	Cu(OAc)₂	17
9	CH₃OH	Zn(OAc)₂	23
10	CH₃OH	AgOAc	78
11	CH₃OH	NaOAc	24
12	CH₃OH	KOAc	31
13^d	CH₃OH	Cu(OAc)₂	80
14^e	CH₃OH	Cu(OAc)₂	34
15	CH₃OH	—	30
16^f	CH₃OH	—	NR

Entry	Product	Yield^b/%
Entry	Product	[Cp*RhCl₂]₂	Cp^AcRh(III)
1	3c	59	84
2	3e	71	90
3	3j	63	87
4	3m	54	79

Entry	Product	Yield^b/%
Entry	Product	[Cp*RhCl₂]₂	Cp^AcRh(III)
1	3c	59	84
2	3e	71	90
3	3j	63	87
4	3m	54	79

Entry	Catalyst	Additive	Yield^b/%
1	Cp^AcRh(III) (5 mol%)	—	52
2	Cp^AcRh(III) (10 mol%)	—	73
3	[Cp^*RhCl₂]₂ (5 mol%)	—	Trace
4	Cp^AcRh(III) (2.5 mol%)	Cu(OTf)₂ (5 mol%)	33
5	[Cp^*RhCl₂]₂ (2.5 mol%)	Cu(OTf)₂ (5 mol%)	Trace
6	Cp^AcRh(III) (2.5 mol%)	NaOAc (5 mol%)	80
7	Cp^AcRh(III) (5 mol%)	AgSbF₆ (10 mol%)	51
8	[Cp^*RhCl₂]₂ (2.5 mol%)	AgSbF₆ (10 mol%)	45