膦氧导向钯催化邻碳硼烷Heck类型的官能团化反应

doi:10.6023/cjoc202103015

摘要/Abstract

邻-碳硼烷的选择性官能团化是碳硼烷化学中的一个热点. 由于邻-碳硼烷特殊的三维芳香性, 其在聚集诱导发光材料、非线性发光材料以及其他功能材料领域有着广泛的应用. 在邻碳硼烷上引入π-共轭体系能进一步扩大其在发光材料领域的应用. 报道了膦氧导向钯催化邻碳硼烷Heck类型的单烯基化反应.

关键词: 钯, Heck反应, 碳硼烷, B—H活化

The selective functionalization of o-carboranes is a popular topic in carborane chemistry. o-Carborane has been widely used in aggregation-induced luminescent materials, nonlinear luminescent materials and other function materials due to its special 3D-aromaticity. The π conjugated systems-tethered o-carboranes could further broaden its applications in the field of luminescent materials. Herein, we have developed a palladium-catalyzed Heck-type mono-alkenylation of o-carboranes featuring phosphine oxide as the directing group.

Key words: palladium, Heck reaction, carborane, B—H activation

引用此文

连凌翔, 尹静怡, 林彩霞, 叶克印, 袁耀锋. 膦氧导向钯催化邻碳硼烷Heck类型的官能团化反应[J]. 有机化学, 2021, 41(8): 3249-3255.

Lingxiang Lian, Jingyi Yin, Caixia Lin, Keyin Ye, Yaofeng Yuan. Phosphine Oxide-Directed Palladium-Catalyzed Heck-Type Functionalization of o-Carboranes[J]. Chinese Journal of Organic Chemistry, 2021, 41(8): 3249-3255.

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图/表 6

Scheme 1. Transition-metal-catalyzed B—H bond functionalization of o-carboranes

Entry	Cat.	Ag salt	x	Yield^b/%
1	Pd(OAc)₂	AgOAc	2	<5
2	Pd(TFA)₂	AgOAc	2	13
3	Pd(OAc)₂	AgTFA	2	21
4	Pd(TFA)₂	AgTFA	2	32
5 ^c	Pd(TFA)₂	AgTFA	3	46
6^c^,^d	Pd(TFA)₂	AgTFA	3	54 (46) ^e

Table 1. Reaction condition optimizationa

Figure 1. X-ray diffraction analysis of 3

Table 2. Substrate scope of the palladium-catalyzed B(4)-alkenylation of o-carboranesa

Scheme 2. Unsuccessful substrates

Scheme 3. Proposed mechanism

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