Synthesis of Zn-Li Bimetallic Compound and Its Catalytic Application in Hydroboration of Isocyanate

doi:10.6023/cjoc202006027

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (1): 357-363.DOI: 10.6023/cjoc202006027 Previous Articles Next Articles

Article

锌-锂双金属化合物的合成及其在异腈酸酯硼氢化中的催化应用

肖钤^a, 臧沈荦^a, 陈泽卫^b, 姚薇薇^b^,^*(), 郑晶^a^,^*(), 马猛涛^a^,^*()

a 南京林业大学理学院南京 210037
b 南京中医药大学药学院南京 210023

收稿日期:2020-06-15 修回日期:2020-07-26 发布日期:2020-08-19
通讯作者: 姚薇薇, 郑晶, 马猛涛
作者简介:
* Corresponding authors. E-mail: yww0715@hotmail.com, jzheng62@njfu.edu.cn, mengtao@njfu.edu.cn
基金资助:
国家自然科学基金(21772093); 国家自然科学基金(21372117); 江苏省自然科学基金(BK20181421); 江苏省研究生科研与实践创新计划(KYCX18_0983)

Synthesis of Zn-Li Bimetallic Compound and Its Catalytic Application in Hydroboration of Isocyanate

Qian Xiao^a, Shenluo Zang^a, Zewei Chen^b, Weiwei Yao^b^,^*(), Jing Zheng^a^,^*(), Mengtao Ma^a^,^*()

a College of Science, Nanjing Forestry University, Nanjing 210037
b College of Pharmacy, Nanjing University of Chinese Medicine, Nanjing 210023

Received:2020-06-15 Revised:2020-07-26 Published:2020-08-19
Contact: Weiwei Yao, Jing Zheng, Mengtao Ma
Supported by:
the National Natural Science Foundation of China(21772093); the National Natural Science Foundation of China(21372117); the Natural Science Foundation of Jiangsu Province(BK20181421); the Postgraduate Research & Practice Innovation Program of Jiangsu Province(KYCX18_0983)

1. cjoc202006027辅助材料.pdf(620KB)

Abstract

There are very few reports on the isocyanate hydroboration. So far, the Zn-catalyzed hydroboration of isocyanate has not been reported. The synthesis of a novel asymmetric β-diketiminate Zn-Li bimetallic compound and its application as a highly efficient catalyst in the hydroboration of various isocyanates with HBpin in high yields are reported. The preliminary mechanism of hydroboration reaction has been explored.

Key words: Zn-Li bimetallic compound, isocyanate, hydroboration, synthesis

Cite this article

Qian Xiao, Shenluo Zang, Zewei Chen, Weiwei Yao, Jing Zheng, Mengtao Ma. Synthesis of Zn-Li Bimetallic Compound and Its Catalytic Application in Hydroboration of Isocyanate[J]. Chinese Journal of Organic Chemistry, 2021, 41(1): 357-363.

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Fig. & Tab. 14

References 30

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Zn(1)–N(1)	0.1976(2)	Zn (1)–N(2)	0.1979(3)
Zn(1)–I(1)	0.2592(4)	Zn (1)–I(2)	0.2660(4)
Li(1)–I(1)	0.2872(6)	Li(1)–I(2)	0.2800(6)
Li(1)–O(1)	0.1927(7)	Li(1)–O(2)	0.1910(7)
N(1)–Zn(1)–N(2)	98.21(11)	I(1)–Zn(1)–I(2)	102.42(15)
N(1)–Zn(1)–I(1)	115.43(7)	N(1)–Zn(1)–I(2)	112.78(7)
N(2)–Zn(1)–I(1)	122.50(7)	N(2)–Zn(1)–I(2)	105.50(7)
Zn(1)–I(1)–Li(1)	80.33(13)	Zn(1)–I(2)–Li(1)	80.53(12)
I(1)–Li(1)–I(2)	92.39(18)	O(1)–Li(1)–O(2)	109.40(3)
I(1)–Li(1)–O(1)	121.90(3)	I(1)–Li(1)–O(2)	108.20(3)
I(2)–Li(1)–O(1)	108.20(3)	I(2)–Li(1)–O(2)	116.40(3)

Zn(1)–N(1)	0.1976(2)	Zn (1)–N(2)	0.1979(3)
Zn(1)–I(1)	0.2592(4)	Zn (1)–I(2)	0.2660(4)
Li(1)–I(1)	0.2872(6)	Li(1)–I(2)	0.2800(6)
Li(1)–O(1)	0.1927(7)	Li(1)–O(2)	0.1910(7)
N(1)–Zn(1)–N(2)	98.21(11)	I(1)–Zn(1)–I(2)	102.42(15)
N(1)–Zn(1)–I(1)	115.43(7)	N(1)–Zn(1)–I(2)	112.78(7)
N(2)–Zn(1)–I(1)	122.50(7)	N(2)–Zn(1)–I(2)	105.50(7)
Zn(1)–I(1)–Li(1)	80.33(13)	Zn(1)–I(2)–Li(1)	80.53(12)
I(1)–Li(1)–I(2)	92.39(18)	O(1)–Li(1)–O(2)	109.40(3)
I(1)–Li(1)–O(1)	121.90(3)	I(1)–Li(1)–O(2)	108.20(3)
I(2)–Li(1)–O(1)	108.20(3)	I(2)–Li(1)–O(2)	116.40(3)

Zn(1)–N(1)	0.2031(18)	Zn(1)–N(2)	0.2033(17)
Zn(1)–N(3)	0.2017(17)	Zn (1)–N(4)	0.2051(17)
N(1)–Zn(1)–N(2)	94.71(7)	N(1)–Zn(1)–N(3)	113.49(7)
N(1)–Zn(1)–N(4)	114.80(7)	N(2)–Zn(1)–N(3)	124.91(7)
N(2)–Zn(1)–N(4)	115.96(7)	N(3)–Zn(1)–N(4)	94.43(7)

Zn(1)–N(1)	0.2031(18)	Zn(1)–N(2)	0.2033(17)
Zn(1)–N(3)	0.2017(17)	Zn (1)–N(4)	0.2051(17)
N(1)–Zn(1)–N(2)	94.71(7)	N(1)–Zn(1)–N(3)	113.49(7)
N(1)–Zn(1)–N(4)	114.80(7)	N(2)–Zn(1)–N(3)	124.91(7)
N(2)–Zn(1)–N(4)	115.96(7)	N(3)–Zn(1)–N(4)	94.43(7)

Compd.	2	3
Formula	C ₃₄H ₅₅I ₂LiN ₂O ₂Zn	C ₁₀₇H ₁₄₇N ₈Zn ₂
M _r	849.91	1676.11
Temp./K	130(2)	120(2)
λ/nm	0.071073	0.071073
Crystal system	Monoclinic	Monoclinic
Space group	P2 ₁/ c	P2 ₁/ n
a/nm	1.15779(9)	1.08285(4)
b/nm	3.0070(2)	2.17902(8)
c/nm	1.24889(9)	4.01324(15)
α/(°)	90	90
β/(°)	116.076(2)	95.7710(10)
γ/(°)	90	90
V/nm ³	3.9054(5)	9.4215(6)
Z	4	4
ρ _calc/(g•cm ^–3)	1.446	1.182
μ/mm ^–1	2.238	0.560
F(000)	1712	3620
R ₁(obs. data)	0.0289	0.0384
wR ₂(obs. data)	0.0629	0.0866
GOF on F ²	1.094	1.030
CCDC	2008454	2008455

锌-锂双金属化合物的合成及其在异腈酸酯硼氢化中的催化应用

Synthesis of Zn-Li Bimetallic Compound and Its Catalytic Application in Hydroboration of Isocyanate

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References 30

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Entry	Cat./mol%	n	Temp./℃	Time/h	Yield ^a /%
1	0	3	25	12	0
2	0	3	60	12	0
3	5	3	25	24	23
4	5	3	60	12	93
5	10	3	60	12	95
6	5	3	60	6	70
7	5	3.5	60	6	99

Entry	Cat./mol%	n	Temp./℃	Time/h	Yield ^a /%
1	0	3	25	12	0
2	0	3	60	12	0
3	5	3	25	24	23
4	5	3	60	12	93
5	10	3	60	12	95
6	5	3	60	6	70
7	5	3.5	60	6	99

Entry	Ar/R	Yield ^a /%	Entry	Ar/R	Yield ^a /%
1 ^b	ⁱ Pr	99	2 ^b	Et	99
3 ^b	ⁿ Pr	99	4 ^b	ⁿ Bu	99
5 ^b	^t Bu	95	6 ^b	Ad	99
7 ^c		94	8 ^c		93
9 ^c		99	10 ^c		99
11 ^c		99	12 ^c		99

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Entry	Cat./mol%	n	Temp./℃	Time/h	Yield ^a /%
1	0	3	25	12	0
2	0	3	60	12	0
3	5	3	25	24	23
4	5	3	60	12	93
5	10	3	60	12	95
6	5	3	60	6	70
7	5	3.5	60	6	99

Entry	Cat./mol%	n	Temp./℃	Time/h	Yield ^a /%
1	0	3	25	12	0
2	0	3	60	12	0
3	5	3	25	24	23
4	5	3	60	12	93
5	10	3	60	12	95
6	5	3	60	6	70
7	5	3.5	60	6	99

Entry	Cat./mol%	n	Temp./℃	Time/h	Yield ^a /%
1	0	3	25	12	0
2	0	3	60	12	0
3	5	3	25	24	23
4	5	3	60	12	93
5	10	3	60	12	95
6	5	3	60	6	70
7	5	3.5	60	6	99

Entry	Cat./mol%	n	Temp./℃	Time/h	Yield ^a /%
1	0	3	25	12	0
2	0	3	60	12	0
3	5	3	25	24	23
4	5	3	60	12	93
5	10	3	60	12	95
6	5	3	60	6	70
7	5	3.5	60	6	99