卡宾催化对亚甲基苯醌的不对称硼化反应的研究

doi:10.6023/cjoc202111041

摘要/Abstract

使用商业化的手性三氮唑盐和联硼酸频哪醇酯[B₂(pin)₂], 实现了N-杂环卡宾催化的对亚甲基苯醌的1,6-不对称硼加成反应. 该反应条件温和, 底物适用范围广, 官能团耐受性好, 且有良好的反应收率及对映选择性. 值得注意的是, 在无过渡金属存在下, 即使催化剂用量降至底物的0.1 mol%, 反应仍能保持高收率和高对映选择性.

关键词: 不对称催化, 有机催化, 卡宾, 硼化合物, 对亚甲基苯醌

The first carbene-catalyzed enantioselective 1,6-conjugate addition of boron to para-quinone methides was achieved by using the commercially available chiral triazolium and bis(pinacolato)diboron. The main features of this reaction include mild conditions, broad scope of substrates, excellent functional group tolerance, as well as good yield and enantioselectivity. Notably, in the absence of any transition metals, the reaction proceeded very well even with 0.1 mol% of catalyst loading without obvious erosion of yield and enantioselectivity, albeit longer reaction time was required.

引用此文

吴逾诸, 申盼盼, 段文增, 马玉道. 卡宾催化对亚甲基苯醌的不对称硼化反应的研究[J]. 有机化学, 2022, 42(5): 1483-1492.

Yuzhu Wu, Panpan Shen, Wenzeng Duan, Yudao Ma. Asymmetric Boration of para-Quinone Methides Catalyzed by N-Heterocyclic Carbene[J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1483-1492.

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Entry	Precatalyst	Time/h	Yield^b/%	er^c
1	(R,R_p)-3	1.5	90	17∶83
2	(S,S_p)-4	3.0	95	82∶18
3	(R)-5	5.0	83	14∶86
4	(5R,10S)-6	0.8	93	86∶14
5	(5R,10S)-7	5.0	85	87∶13
6	(S)-8	0.7	95	83∶17
7	(S)-9	1.0	86	82∶18
8	(S)-10	5.0	62	73∶27
9	(S)-11	0.8	91	86∶14
10	(S)-12	1.0	90	81∶19
11	(S)-13	0.8	95	91∶9

Entry	Precatalyst	Time/h	Yield^b/%	er^c
1	(R,R_p)-3	1.5	90	17∶83
2	(S,S_p)-4	3.0	95	82∶18
3	(R)-5	5.0	83	14∶86
4	(5R,10S)-6	0.8	93	86∶14
5	(5R,10S)-7	5.0	85	87∶13
6	(S)-8	0.7	95	83∶17
7	(S)-9	1.0	86	82∶18
8	(S)-10	5.0	62	73∶27
9	(S)-11	0.8	91	86∶14
10	(S)-12	1.0	90	81∶19
11	(S)-13	0.8	95	91∶9

Entry	Base	Base/mol%	Time/h	Yield^d/%	er^e
1	DBU	30.0	0.8	95	91∶9
2^b	DBU	30.0	3.0	94	91∶9
3	CsCO₃	30.0	0.3	93	91∶9
4	K₂CO₃	30.0	0.5	94	93∶7
5	TBD	30.0	1.2	90	92∶8
6	C₃H₁₀KOSi	30.0	0.8	92	88∶12
7	K₂CO₃	60.0	0.2	85	92∶8
8	K₂CO₃	15.0	0.3	95	94∶6
9	K₂CO₃	7.5	1.0	88	94∶6
10^c	K₂CO₃	15.0	7.0	84	94∶6

Entry	Base	Base/mol%	Time/h	Yield^d/%	er^e
1	DBU	30.0	0.8	95	91∶9
2^b	DBU	30.0	3.0	94	91∶9
3	CsCO₃	30.0	0.3	93	91∶9
4	K₂CO₃	30.0	0.5	94	93∶7
5	TBD	30.0	1.2	90	92∶8
6	C₃H₁₀KOSi	30.0	0.8	92	88∶12
7	K₂CO₃	60.0	0.2	85	92∶8
8	K₂CO₃	15.0	0.3	95	94∶6
9	K₂CO₃	7.5	1.0	88	94∶6
10^c	K₂CO₃	15.0	7.0	84	94∶6