PERIPHERAL MERCURATION OF METALLOPORPHYRINS - NOVEL SYNTHESES OF DEOXOPHYLLOERYTHROETIOPORPHYRIN AND DEOXOPHYLLOERYTHRIN METHYL-ESTER
PERIPHERAL MERCURATION OF METALLOPORPHYRINS - NOVEL SYNTHESES OF DEOXOPHYLLOERYTHROETIOPORPHYRIN AND DEOXOPHYLLOERYTHRIN METHYL-ESTER
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DOI：
10.1021/jo00198a006
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发表时间：
1984-01-01
影响因子：
3.6
通讯作者：
MINNETIAN, OM
中科院分区：
文献类型：
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作者：
SMITH, KM;LANGRY, KC;MINNETIAN, OM
C 02 Me红初卟啉（2）（DPEP），和（c）“rhodo型”系列，其已显示具有苯并卟啉骨架。最近，从Serpiano等油页岩中分离出一种7，7-丁卟啉，3从Julia Creek油页岩中分离出2-去乙基-DPEP和三种7，7-丁卟啉的镍（II）配合物。[4]长期以来，人们一直认为石油矿床中的卟啉是由叶绿素随时间降解而产生的，[5-7]而最近的证据[4]似乎支持这一论点。光谱学工作得出结论8，DPEP（2）、脱氧叶红蛋白及其甲酯3存在于德国梅塞尔油页岩中。实际上，DPEP是以非常低的产率从脱镁叶绿素制备的。9为了满足对纯的石油卟啉标记物的需要，已经描述了由三吡咯合成DPEP的几种方法。从吡咯亚甲基10，11出发的两种方法得到了产率很低的DPEP，并且具有不同的电子吸收光谱。第三种合成方法，12产率为6%，由带有完整环外环的α-联二烯进行，代表了显著的改进;最近，Clezy和同事13描述了DPEP的合成，其中通过酮酯和铊（III）促进的环化将环外环加入到预先形成的卟啉中。本文描述了一种新的合成DPEP（2）[通过吡咯杂卟啉XV（4）]和脱氧叶红蛋白甲酯（3）的方法，其中通过汞化/钯-烯烃反应在预形成的卟啉上构建麻烦的环外环。次卟啉IX二甲酯，（5）]与醋酸汞反应得到相应的汞化卟啉，例如6。随后在乙腈中与LiPdCl 3反应，然后与丙烯酸甲酯反应，得到双丙烯酸酯7。用NaBD 4对6进行脱汞显示14，5例中的6例（约125%）是由于所需产品被相应的内消旋汞化衍生物污染;此外，形成两种“单丙烯酸酯”副产物，其结构当时未指定，提供了一些意想不到的副反应的证据，在另一方面，从汞化卟啉形成干净的丙烯酸酯。在较早的工作中，使用4摩尔当量的乙酸汞，得到双丙烯酸酯7的产率为37%，而“单丙烯酸酯”的合并产率为25%。随后使用6摩尔当量的乙酸汞得到48%的“单丙烯酸酯”的合并产率，相比之下，双丙烯酸酯7的合并产率仅为25%。醋酸汞过量会导致所有产物的产率降低。
C02Me erythroetioporphyrin (2)(DPEP), and (c) a “rhodo-type” series, which has been shown2 to possess a benzoporphyrin skeleton. Recently, a 7, 7-butanoporphyrin has been iso-lated from Serpiano and other oil shales, 3 and the nickel (II) complexes of 2-desethyl-DPEP and three 7, 7-butanoporphyrins have been isolated from Julia Creek oil shales. 4 Porphyrins which occur in petroleumdeposits have long been believed to be derived by degradation of chlorophyll over the course of time, 5-7 and recent evidence4 appears to support this contention. Spectroscopic work has re-sulted in the conclusion8 that DPEP (2), deoxophyllo-erythrin, and itsmethyl ester, 3, are present in German Messel oil shale. Indeed, DPEP has been prepared in very low yield from pheophytin. 9 In response to a need for pure petroporphyrin markers, several syntheses of DPEP from monopyrroles have been described. Two approaches from pyrromethenes10, 11 gave DPEP in miniscule yieldsand with differing electronic absorption spectra. A third synthesis, 12 in 6% yield, from a-bilene bearing the intact exocyclic ring represented a dramatic improvement; most recently, Clezy and co-workers13 have described a synthesis of DPEP in which the exocyclic ring was added to a preformed porphyrin by way of a keto ester and thallium (III)-pro-moted cyclization. In this paper we describe a novel synthesis of DPEP (2)[by way of pyrroetioporphyfin XV (4)] and deoxyphylloerythrin methyl ester (3) in which the troublesome exocyclic ring is constructed on preformed porphyrins by way of a mercuration/palladium-olefin reaction.Results and Discussion It has previously been shown14 that zinc (II) or copper (II) derivatives of ß-unsubstituted porphyrins [such as zinc (II) deuteroporphyrin IX dimethyl ester,(5)] react with mer-curic acetate to give the corresponding mercurated porphyrin, eg, 6. Subsequent reaction with LiPdCl3 in ace-tonitrile and then with methylacrylate gave the bis acrylate 7. Demercuration of 6 with NaBD4 showed14 that the excessively high yields (approximately 125%) of 6 from 5 were due to contamination of the required product with the corresponding meso-mercurated derivatives; moreover, formation of two “monoacrylate” byproducts, the struc-tures of which were at that time unassigned, provided evidence of some unexpected side reactions in the other-wise clean acrylateformation from the mercurated porphyrin. In the earlier work14 4 molar equiv of mercuric acetate were used and a 37% yield of the bis acrylate 7 was obtained, compared with a combined yield of 25% for the “monoacrylates”. Subsequent use of 6 molar equiv of mercuric acetate afforded a combined yield of 48% of the “monoacrylates”, compared with only 25% of the bis acrylate 7. Larger excesses of mercuric acetate resulted in lowering of yields of all products.