Total synthesis of the chlorine-containing hapalindoles K, A, and G.
Total synthesis of the chlorine-containing hapalindoles K, A, and G.
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含氯的Hapalindoles K，A和G的总合成。
DOI：
10.1002/anie.201100957
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发表时间：
2011-08-08
影响因子：
16.6
通讯作者：
Johnston, Jeffrey N.
中科院分区：
文献类型：
--
作者：
Chandra, Aroop;Johnston, Jeffrey N.
陆地蓝绿藻的吲哚生物碱[1]引起了广泛的反应，以新的化学方法和制备这些结构多样的天然产物的形式。这一事业的驱动力，部分是由不同的生物活性，往往是与他们的居民蓝藻代谢产物。[2]从Natalism的（非氯化）hapalindoles J & M的合成开始，[3] fischerindole，[4] hapalindole，[3，5] welwitindolinone，[4，6]和ambigine [7]天然产物的成员已经通过全化学合成获得。[8]氯化同系物进一步增加了这类天然产品的功能和立体化学多样性，但其合成解决方案的数量很少。Fukuyama首次报道了含有手性仲烷基氯的hapalindole（hapalindole G，3）的合成。[5g]氯和甲基之间的顺式关系是通过氯化锂使环丙烷开环而建立的。2005年，Baran和同事报道了合成fischerindoles I和G。这些线性四环的新戊基氯是非对映异构体相对于在3中，并且还通过一系列立体特异性转化，导致环氧开环反应构建。[4]同样的新戊基氯也包含在welwitindolinone A中，Wood对此的解决方案涉及氯诱导的[1，2]-甲基位移，以建立甲基和氯之间的反关系。同样出色的是Baran小组从（−）-fischerindole制备（+）-welwitindolinone A
The indole alkaloids of the terrestrial blue-green algae [1] have elicited a broad response in the form of new chemical methods and preparations for these structurally diverse natural products. This enterprise is driven, in part, by the diverse biological activity that is often associated with metabolites of their resident cyanobacteria.[2] Beginning with Natsume's syntheses of (nonchlorinated) hapalindoles J & M,[3] members of the fischerindole,[4] hapalindole,[3, 5] welwitindolinone,[4, 6] and ambiguine [7] natural products have been accessed by total chemical synthesis.[8] The chlorinated congeners further increase the functional and stereochemical diversity of this natural product class, but solutions for their synthesis are few in number. Fukuyama reported the first synthesis of a hapalindole containing a chiral secondary alkyl chloride (hapalindole G, 3).[5g] The syn relationship between the chlorine and methyl groups was established by cyclopropane ring opening with lithium chloride. In 2005, Baran and coworkers reported syntheses of fischerindoles I and G. The neopentyl chloride of these linear tetracycles is diastereomeric relative to that in 3, and was also constructed through a series of stereospecific transformations, leading with an epoxide ring opening reaction.[4] The same neopentyl chloride is contained within welwitindolinone A, and Wood's solution to this involved a chloronium-induced [1, 2]-methyl shift to establish the anti-relationship between the methyl and chlorine. Equally elegant was the Baran group's preparation of (+)-welwitindolinone A from (−)-fischerindole
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影响因子：
64.8
作者：
Baran, Phil S.;Maimone, Thomas J.;Richter, Jeremy M.
通讯作者：
Richter, Jeremy M.
影响因子：
5.1
作者：
Mo, Shunyan;Krunic, Aleksej;Chlipala, George;Orjala, Jimmy
通讯作者：
Orjala, Jimmy
影响因子：
15
作者：
Reisman, Sarah E.;Ready, Joseph M.;Wood, John L.
通讯作者：
Wood, John L.
影响因子：
15
作者：
Kinsman, AC;Kerr, MA
通讯作者：
Kerr, MA
影响因子：
15
作者：
MOORADIAN, A;CLOKE, JB
通讯作者：
CLOKE, JB