6种松毛虫性信息素前体化合物全合成研究进展

doi:10.11707/j.1001-7488.20200419

摘要/Abstract

摘要：

目前，我国有6种松毛虫对松林危害严重，包括马尾松毛虫、落叶松毛虫、油松毛虫、云南松毛虫、赤松毛虫和思茅松毛虫。松毛虫具有很强的繁殖能力，暴发成灾时针叶被全部吃光，严重阻碍林木生长，甚至致其成片死亡；松毛虫危害导致树势衰弱后还容易引起蛀干害虫入侵，造成松树进一步大面积死亡，寻找有效的种群监测手段是对松毛虫进行综合治理的重要环节。利用性信息素防治害虫具有特异性强、使用简便等优点，是松毛虫类害虫综合治理措施中的一个重要手段。性信息素引诱剂不仅可以用于松毛虫成虫发生期及种群动态的监测，而且还有可能通过干扰其交配控制其种群数量和猖獗发生。目前，6种松毛虫性信息素成分主要包括，顺，反-5，7-十二碳二烯-1-醇衍生物和反，顺-5，7-十二碳二烯-1-醇衍生物两大类。其前体化合物分别为顺，反-5，7-十二碳二烯-1-醇和反，顺-5，7-十二碳二烯-1-醇。顺，反-5，7-十二碳二烯-1-醇主要有3种不同的合成路线：1) Wittig反应，即膦盐与醛的反应；2)碘代烯的偶联反应，即E型碘代烯烃与不饱和烃偶联反应；3)其他类型反应，即包括烯烃与炔烃类化合物的反马氏加成、乙基烯基炔基硼烷重排以及有机金属试剂偶联等反应。反，顺-5，7-十二碳二烯-1-醇的主要合成方法包括：1) Wittig反应，即α，β-不饱和醛与膦盐反应；2)E型碘代烯醇与炔烃偶联反应。当前，松毛虫性信息素的需求量日益增加，对其合成方法进一步设计、优化成为亟需开展的重要课题。

关键词: 松毛虫属, 性信息素, 顺,反-5, 7-十二碳二烯-1-醇, 反,顺-5, 7-十二碳二烯-1-醇, 全合成

Abstract:

There are six species of pine caterpillars in China,including pine caterpillars include Dendrolimus punctatus,D. superans,D. tabulaeformis,D. houi,D. spectabilis and D. kikuchii,and all the insects are serious pests of pine forests in China. Pine caterpillars have a strong reproductive capacity. When the pests break out,the all leaves of pines are eaten up quickly,which seriously hinders the growth of trees and even causes the trees to die. Furthermore,the pine caterpillars'infestation cause pines to decline,which can lead to the invasion of stem borers. Therefore,the control of pine caterpillars has always been an important research direction of forest entomologists in China. It is an important part of the comprehensive management of pine caterpillars to find an effective population monitoring method. Sex pheromone is an important means for the comprehensive management of pine caterpillars for its strong specificity and convenient application. Sex pheromone attractants can be used not only to monitor the occurrence period and population dynamics of pine caterpillars,but also to control the population number and prevalence by interfering with their mating. The active ingredients of sex pheromones in the 6 species of pine caterpillars could be divided into two main categories. The derivative of (Z,E)-5,7-dodecadien-1-ol and the derivative of (E,Z)-5,7-dodecadien-1-ol. Their precursors are the corresponding alcohols. In this paper,the synthesis methods of these two precursor compounds were summarized. The total synthesis of (Z,E)-5,7-dodecadien-1-ol could be roughly classified into three different synthetic ways. Route one,the Wittig reaction between aldehydes and phosphoranes; Route two,coupling reaction of E type iodinated alkene with unsaturated hydrocarbons; Other paths of reactions,including anti-Markovnikov addition of substituted olefins; rearrangement of thexylalkenyllalkynylboranes,and coupling reactions of organometallic reagents. In contrast,(E,Z)-5,7-dodecadien-1-ol could be synthesized by two ways. Route one,the Wittig reaction between α,β-unsaturated aldehydes and phosphoranes; Route two,coupling reaction of E type iodinated enol with alkynes. At present,the demand for sex pheromone of pine caterpillars is increasing day by day,and the design and optimization of its synthesis methods have become an important task. Consequently,this review will provide important reference for the researchers who carry out the similar research in China.

Key words: Dendrolimus spp., sex pheromone, (Z, E)-5, 7-dodecadien-1-ol, (E, Z)-5, 7-dodecadien-1-ol, total synthesis

中图分类号:

S763.3

刘福,袁中伟,孔祥波,张苏芳,张真,国志峰,李振林,宋艳辉,周益彬. 6种松毛虫性信息素前体化合物全合成研究进展[J]. 林业科学, 2020, 56(4): 170-180.

Fu Liu,Zhongwei Yuan,Xiangbo Kong,Sufang Zhang,Zhen Zhang,Zhifeng Guo,Zhenlin Li,Yanhui Song,Yibin Zhou. Research Progress on Total Synthesis of Precursor Components of Sex Pheromones from Six of Pine Caterpillar Species in China[J]. Scientia Silvae Sinicae, 2020, 56(4): 170-180.

图/表 11

表1

顺,反-5, 7-十二碳二烯-1-醇的合成路线①"

原料 Start materials	合成步骤 Steps	总产率 Overall yield(%)	构型 Configuration	文献 References
2-庚炔-1-醇2-Heptyn-1-ol	6	—	Z5, E7;E5, E7	孟宪佐, 1982 Meng X Z, 1982；孟宪佐等, 1983 Meng X Z et al., 1983
1, 5-戊二醇1, 5-Pentanediol	7	—	Z5, E7;Z5, Z7	Ando et al., 1985
戊醛、(甲酰甲基)三苯基砷盐Valeraldehyde, (Formylmethy1)triphenylarsonium Bromide	4	51	Z5, E7	Huang et al., 1987
乙炔、丙烯醛Ethyne, Acrolein	7	9	Z5, E7	陶云海等, 2005a Tao Y H et al., 2005a
1-溴-顺-2-庚烯的三苯基膦盐、5-乙酰氧戊醛(Z)-2- heptenyl triphenylph osphonium bromide, 5-Acetoxypentanal	1	—	Z, Z;Z, E;E, Z;E, E	Chisholm et al., 1981
1-己炔、2-(4-氯丁氧基)四氢-2H-吡喃1-Hexyne, 2-(4-chlorobutoxy)tetrahydro-2H-pyran	5	31.5	Z5, E7	Ando et al., 1982
1-己炔、5-己炔-1-醇1-Hexyne, 5-Hexyn-1-ol	5	34.4	Z5, E7	Rossi, 1983
1-溴-4-(2-乙氧基乙基)丁烷1-Bromo-4- (2-ethoxyethyl) butane	6	—	Z5, E7	Gardette et al., 1984
1-己炔、5-己炔-1-醇1-Hexyne, 5-Hexyn-1-ol	5	51.7	Z5, E7	Stille et al., 1987
1-己炔、三甲基烯丙基硅烷1-Hexyne, Allyltrimethylsilane	7	—	Z5, E7	孙小静等, 1990 Sune X J et al., 1990
2-(6-庚炔氧基)四氢-2H-吡喃、反-1-碘代己烯2-(6-heptanyloxy)tetrahydro-2H-pyran, (E)-1-Iodo-1-hexene	3	—	Z5, E7	Khrimian et al., 2002
四氢吡喃、1-己炔Tetrahydropyran, 1-Hexyne	9	14.5	Z5, E7	张玉顺, 2001 Zhang Y X, 2001；古昆等, 2004 Gu K et al., 2004
1-己烯、叔丁基(5-己炔氧基)二甲基硅烷1-Hexyne, t-Butyl(5-hexanyloxy) dimethylsilane	4	36.2	Z5, E7	Trost et al., 1984
1-戊炔1-Pentyne	6	—	Z5, E7	Brown et al., 1986
苯基硫代乙炔、铜锂试剂Phenylthioacefylene, Lithium organocuprates	3	57	Z5, E7	Fiandanese et al., 1989
丙炔醇、2-(4-溴丁氧基)四氢-2H-吡喃Propargyl alcohol, 2-(4-BroMobutoxy)terahydro-2H-pyran	7	13.4	Z5, E7	Vig et al., 1990

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