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General Approach for the Synthesis of Sarpagine Indole Alkaloids. Enantiospecific Total Synthesis of (+)-Vellosimine, (+)-Normacusine B, (−)-Alkaloid Q<sub>3</sub>, (−)-Panarine, (+)-<i>N</i><sub>a</sub>-Methylvellosimine, and (+)-<i>N</i><sub>a</sub>-Methyl-16-epipericyclivine

Jianming YuDepartment of Chemistry, University of WisconsinMilwaukee, Milwaukee, Wisconsin 53201, and Laboratory for the Structure of Matter, Code 6030, Naval Research Laboratory, 4555 Overlook Avenue, Washington, D.C. 20375Tao WangDepartment of Chemistry, University of WisconsinMilwaukee, Milwaukee, Wisconsin 53201, and Laboratory for the Structure of Matter, Code 6030, Naval Research Laboratory, 4555 Overlook Avenue, Washington, D.C. 20375Xiaoxiang LiuDepartment of Chemistry, University of WisconsinMilwaukee, Milwaukee, Wisconsin 53201, and Laboratory for the Structure of Matter, Code 6030, Naval Research Laboratory, 4555 Overlook Avenue, Washington, D.C. 20375Jeffrey R. DeschampsDepartment of Chemistry, University of WisconsinMilwaukee, Milwaukee, Wisconsin 53201, and Laboratory for the Structure of Matter, Code 6030, Naval Research Laboratory, 4555 Overlook Avenue, Washington, D.C. 20375Judith Flippen‐AndersonDepartment of Chemistry, University of WisconsinMilwaukee, Milwaukee, Wisconsin 53201, and Laboratory for the Structure of Matter, Code 6030, Naval Research Laboratory, 4555 Overlook Avenue, Washington, D.C. 20375Xuebin LiaoDepartment of Chemistry, University of WisconsinMilwaukee, Milwaukee, Wisconsin 53201, and Laboratory for the Structure of Matter, Code 6030, Naval Research Laboratory, 4555 Overlook Avenue, Washington, D.C. 20375James M. CookDepartment of Chemistry, University of WisconsinMilwaukee, Milwaukee, Wisconsin 53201, and Laboratory for the Structure of Matter, Code 6030, Naval Research Laboratory, 4555 Overlook Avenue, Washington, D.C. 20375
2003en
ABI

Аннотация

The first total synthesis of (+)-Na-methyl-16-epipericyclivine (9) was completed [from d-(+)-tryptophan methyl ester] in an overall yield of 42% (eight reaction vessels). The optical rotation [[α]D +22.8 (c 0.50, CHCl3)] obtained on this material confirmed that the reported optical rotation [[α]D 0 (c 0.50, CHCl3)]47 was biogenetically unreasonable. The total syntheses of (+)-vellosimine, (+)-normacusine B, (−)-alkaloid Q3, (−)-panarine, and (+)-Na-methylvellosimine are also described. Moreover, a mixed sample (1:1) of synthetic (−)-panarine and natural (−)-panarine yielded only one set of signals in the 13C NMR; this indicated that the two compounds are identical and further confirmed the correct configuration of (+)-vellosimine, (+)-normacusine B, and (−)-alkaloid Q3. In this approach, the key templates, (−)-Na-H,Nb-benzyltetracyclic ketone 15a and (−)-Na-methyl,Nb-benzyltetracyclic ketone 43 were synthesized on multihundred gram scale by the asymmetric Pictet−Spengler reaction and a stereocontrolled Dieckmann cyclization via improved sequences. An intramolecular palladium (enolate-mediated) coupling reaction was employed to introduce the C(19)−C(20) E-ethylidene function in the sarpagine alkaloids for the first time in stereospecific fashion.

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DOI
10.1021/jo030006h

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Цитирований: 2Использованных источников: 0
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