牛血清白蛋白:一种催化四组分反应合成吡喃[2,3-c]并吡唑类化合物的高效和绿色生物催化剂

doi:10.1016/S1872-2067(15)61088-9

催化学报 ›› 2016, Vol. 37 ›› Issue (9): 1461-1468.DOI: 10.1016/S1872-2067(15)61088-9

牛血清白蛋白:一种催化四组分反应合成吡喃[2,3-c]并吡唑类化合物的高效和绿色生物催化剂

黄杏甜^a, 李志鹏^b, 王东阳^b, 李毅群^a,b

a. 暨南大学生命科学技术学院, 广东广州 510632;
b. 暨南大学化学系, 广东广州 510632

收稿日期:2016-03-06 修回日期:2016-03-24 出版日期:2016-09-21 发布日期:2016-09-21
通讯作者: Yiqun Li
基金资助:
国家自然科学基金（21372099，21072077）；广东省自然科学基金（10151063201000051，8151063201000016）.

Bovine serum albumin: An efficient and green biocatalyst for the one-pot four-component synthesis of pyrano[2,3-c]pyrazoles

Xingtian Huang^a, Zhipeng Li^b, Dongyang Wang^b, Yiqun Li^a,b

a. College of Life Science and Technology, Jinan University, Guangzhou 510632, Guangdong, China;
b. Department of Chemistry, Jinan University, Guangzhou 510632, Guangdong, China

Received:2016-03-06 Revised:2016-03-24 Online:2016-09-21 Published:2016-09-21
Contact: Yiqun Li
Supported by:
This work was supported by the National Natural Science Foundation of China(21372099, 21072077), and the the Natural Science Foundation of Guangdong Province(10151063201000051, 8151063201000016).

摘要/Abstract

摘要：

多组分反应（MCRs）是通过一锅法同时或先后加入3种或3种以上起始原料合成目标产物的过程，具有原子经济性高、化学键构造效率高和反应选择性高等优点，而且可以避免中间体分离和纯化，从而减少废物产生，节省时间，简化分离纯化过程.MCRs由于其灵活性和高效性超过了传统多步合成方法，已成为构建结构新颖的多样性有机分子的新兴工具，尤其是在新药开发中具有广泛应用.吡喃[2,3-c]并吡唑是一类重要杂环化合物，是许多重要新兴药物的关键内核，这些药物具有抑制人类Chk1激酶活性、抗肿瘤活性、止痛镇痛活性、抗菌活性和抗炎活性等.目前已有通过三组分反应（3CRs）、四组分反应（4CRs）乃至五组分反应（5CRs）合成吡喃[2,3-c]并吡唑的文献报道.所用催化剂大多为无机或有机碱性催化剂，所报道的多组分反应或多或少存在一些不足，如反应条件苛刻、所使用试剂昂贵和不易获得、使用定量的催化剂、产率不理想及操作繁琐等.牛血清白蛋白（BSA）是一种来源于牛，在生物体系中没有天然催化功能的廉价易得的非酶转运蛋白.由于生物催化剂如蛋白质、酶及完整细胞等具有催化效率高、选择性高和操作简单等优点，将生物催化剂用于催化有机反应已成为化学领域的研究热点.在这些生物催化剂中，BSA能催化一系列有机反应，包括还原反应、Knoevenagel缩合、aldol缩合、Morita-Baylis-Hillman反应和Biginelli反应等.考虑到吡喃[2,3-c]并吡唑衍生物的重要性以及BSA催化有机反应的多样性，我们设想利用生物催化剂BSA催化4CRs合成吡喃[2,3-c]并吡唑衍生物，即在45℃下，于90%乙醇水溶液中，催化量BSA催化乙酰乙酸乙酯、水合肼、丙二腈和羰基化合物反应.反应完成后，产物经乙醇重结晶纯化，BSA可回收重复使用，重复使用5次，催化活性基本保持不变.在优化条件下，合成了22个吡喃[2,3-c]并吡唑衍生物或及其螺环衍生物.迄今为止，该法尚未见文献报道.总之，我们发展了一种新颖和有效的BSA催化构建结构多样性吡喃[2,3-c]并吡唑衍生物的绿色方法.该法具有环境友好、反应条件温和、反应时间短、产率高和操作简单等优点.同时，该法底物适应范围广，可以使用各种羰基化合物为起始原料，这使它成为一种高效实用的合成结构多样性吡喃[2,3-c]并吡唑衍生物的方法.

关键词: 牛血清白蛋白, 生物催化剂, 多组分反应, 吡喃[2,3-c]并吡唑, 生物催化多样性

Abstract:

The use of biocatalysts is attracting an increasing amount of attention in chemical catalysis. Here, we have shown that bovine serum albumin(BSA), a ubiquitous, inexpensive, non-enzymatic transport protein, can serve as an efficient, retrievable catalyst in the one-pot four-component reaction of aryl aldehydes, malononitrile, hydrazine hydrate, and ethyl acetoacetate for the synthesis of pyrano[2,3-c]pyrazoles under mild reaction conditions. The BSA biocatalyst also displayed a high catalytic affinity for acyclic/cyclic ketones to yield the corresponding pyrano[2,3-c]pyrazoles or their spirocyclic variants. The BSA could be used for at least five cycles without serious loss of catalytic activity. This novel, efficient protocol has the merits of high yield, operational simplicity, and a relatively benign environmental impact. Moreover, the method extends the promiscuity of BSA as a biocatalyst.

Key words: Bovine serum albumin, Biocatalyst, Multicomponent reaction, Pyrano[2,3-c]pyrazole, Biocatalytic promiscuity

黄杏甜, 李志鹏, 王东阳, 李毅群. 牛血清白蛋白:一种催化四组分反应合成吡喃[2,3-c]并吡唑类化合物的高效和绿色生物催化剂[J]. 催化学报, 2016, 37(9): 1461-1468.

Xingtian Huang, Zhipeng Li, Dongyang Wang, Yiqun Li. Bovine serum albumin: An efficient and green biocatalyst for the one-pot four-component synthesis of pyrano[2,3-c]pyrazoles[J]. Chinese Journal of Catalysis, 2016, 37(9): 1461-1468.

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牛血清白蛋白:一种催化四组分反应合成吡喃[2,3-c]并吡唑类化合物的高效和绿色生物催化剂

Bovine serum albumin: An efficient and green biocatalyst for the one-pot four-component synthesis of pyrano[2,3-c]pyrazoles

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