镍催化杂芳烃的非天然戊烯基化及环状单萜化反应

doi:10.1016/S1872-2067(23)64437-7

摘要/Abstract

摘要：

萜类化合物, 如半萜类和单萜类, 是天然产物中种类最繁多、结构最多样的一类, 广泛存在于植物和海洋生物中, 在人类的日常生活中具有重要的应用价值. 自然界中, 二甲基烯丙基焦磷酸酯(DMAPP)和异戊烯基焦磷酸酯(IPP)在各种酶的作用下经过偶联、重排、环化以及异构化等反应合成萜类化合物. 传统的人工方法大多依赖于过渡金属催化的异戊烯基以及反异戊烯基前体的反应, 该反应不仅需要当量的金属试剂, 且反应过程中也会产生当量的副产物, 不符合绿色环保以及原子经济性原则. 异戊二烯作为一种廉价易得的大宗化学品, 其高附加值转化一直是学术界和工业界关注的焦点. 但由于异戊二烯具有反应活性低以及区域选择性调控难的特点, 氢芳基化产物最多可达到十四种异构体. 此外, 异戊二烯容易发生二聚、三聚以及调聚等反应, 产生复杂产物. 上述问题使得异戊二烯的高附加值转化具有很大挑战性.

在前期关于异戊二烯氢官能团化以及手性二聚研究的基础上, 本文提出了一种以异戊二烯为原料, 通过接力催化策略, 在杂芳环中引入非天然戊烯基和环状单萜骨架的方法. 具体而言, 使用廉价金属镍作为催化剂, 小位阻的氮杂环卡宾作为配体, 在当量碱的条件下, 通过马氏加成得到异戊二烯4,3-氢杂芳基化产物, 该策略具有广泛的底物普适性, 较好的选择性和产率. 机理研究表明, 反应首先经过杂环化合物的C-H键氧化加成, 再通过异戊二烯的配位以及迁移插入, 最后通过还原消除获得目标产物. 反应过程中没有当量副产物生成, 符合原子经济性原则. 而当体系中加入当量碱时, 4,3-氢杂芳基化产物通过原位异构化获得了含有四取代烯烃的非天然半萜. 机理研究表明, 碱诱导的异构化和镍催化的分子内氢迁移的机理可能同时存在. 进一步研究表明, 通过控制不同位阻卡宾配体的添加过程, 可以实现“一锅两步法”生成含有四取代烯烃的半萜衍生物和环状单萜衍生物; 具体为先加入小位阻卡宾配体催化生成四取代烯烃, 再加入大位阻卡宾配体以及杂环化合物, 催化生成环状单萜衍生物.

综上, 本文不仅有助于大宗化学品异戊二烯的高效转化, 而且发展的配体调控为半萜类化合物和单萜类化合物的发散性合成提供了新思路, 具有潜在的应用价值.

关键词: 萜类化合物, 异戊二烯, 非天然戊烯基化, 镍催化, 氮杂环卡宾配体, 四取代烯烃

Abstract:

Terpenoids, such as hemiterpenoids and monoterpenoids, are the largest class of natural products, which widely exist in plants and marine organisms. Herein, a divergent strategy is developed for the introduction of unnatural prenyl and cyclic monoterpene skeleton through relay catalysis from basic feedstock isoprene. In the presence of catalytic amount of base, the unnatural prenylation of heteroarenes proceeds through Markovnikov addition onto isoprene with less hindered NHC (IMes) ligand under Ni catalysis. With the aid of extra base, a further in situ isomerization of Markovnikov addition products delivered unnatural hemiterpenoids with tetrasubstituted alkene motif in high selectivities. It was found that bulky NHC (IPr) ligand could further promote sequential hydroheteroarylation between isoprene dimers and heterocycles and gave monoterpenoids in one pot. This work provides a new strategy for regulating the synthesis of hemiterpenoids and monoterpenoids.

Key words: Terpenoid, Isoprene, Unnatural prenylation, Nickel catalysis, N-heterocyclic carbene ligand, Tetrasubstituted alkene

张功, 张炜松, 王小雨, 杨洋, 季定纬, 万伯顺, 陈庆安. 镍催化杂芳烃的非天然戊烯基化及环状单萜化反应[J]. 催化学报, 2023, 49: 123-131.

Gong Zhang, Wei-Song Zhang, Xiao-Yu Wang, Yang Yang, Ding-Wei Ji, Boshun Wan, Qing-An Chen. Ni-catalyzed unnatural prenylation and cyclic monoterpenation of heteroarenes with isoprene[J]. Chinese Journal of Catalysis, 2023, 49: 123-131.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64437-7

https://www.cjcatal.com/CN/Y2023/V49/I6/123

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Entry ^a	Ligand	Base (mol%)	3a (%)	4a (%)	5a ^c (%)	6a ^c (%)	7a (%)	8a (%)	9a (%)
1	L1	^tBuONa (10)	12	0	15/5	0	3	0	0
2	L2	^tBuONa (10)	0	0	0	0	0	0	0
3	L3	^tBuONa (10)	28	0	10/4	0	2	2	0
4	L4	^tBuONa (10)	13	0	0	0	0	0	0
5	L5	^tBuONa (10)	13	0	0	0	0	0	28
6	L6	^tBuONa (10)	82	1	4/5	0	3	0	0
7	L7	^tBuONa (10)	0	0	0	0	0	0	0
8	L6	^tBuOLi (10)	0	0	0	0	0	0	0
9	L6	MeONa (10)	60	0	5/6	0	3	0	0
10	L6	^tBuONa (50)	0	11	0	16/10	0	1	0
11 ^b	L6	^tBuONa (100)	0	14	0	34/18	0	2	0
12 ^b	L6	EtONa (100)	6	81	0	7/4	0	2	0
13 ^b	L6	MeONa (100)	29	43	0	11/6	0	2	0

Entry ^a	Ligand	Base (mol%)	3a (%)	4a (%)	5a ^c (%)	6a ^c (%)	7a (%)	8a (%)	9a (%)
1	L1	^tBuONa (10)	12	0	15/5	0	3	0	0
2	L2	^tBuONa (10)	0	0	0	0	0	0	0
3	L3	^tBuONa (10)	28	0	10/4	0	2	2	0
4	L4	^tBuONa (10)	13	0	0	0	0	0	0
5	L5	^tBuONa (10)	13	0	0	0	0	0	28
6	L6	^tBuONa (10)	82	1	4/5	0	3	0	0
7	L7	^tBuONa (10)	0	0	0	0	0	0	0
8	L6	^tBuOLi (10)	0	0	0	0	0	0	0
9	L6	MeONa (10)	60	0	5/6	0	3	0	0
10	L6	^tBuONa (50)	0	11	0	16/10	0	1	0
11 ^b	L6	^tBuONa (100)	0	14	0	34/18	0	2	0
12 ^b	L6	EtONa (100)	6	81	0	7/4	0	2	0
13 ^b	L6	MeONa (100)	29	43	0	11/6	0	2	0