First Total Synthesis of Cytotoxic Diarylheptanoids, Galeon, and Pterocarine

Wang, Qian; Son, Jong‐Keun; Jahng, Yurngdong

doi:10.1080/00397910601131015

Cited by 13 publications

(6 citation statements)

References 33 publications

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“…Compound 2 was originally reported as pterocarine 21 and its total synthesis has been published. 9 After comparing the published 1 H and 13 C NMR data of engelhardione and pterocarine, we found that the reported spectroscopic data of engelhardione were, indeed, consistent with those of pterocarine. To further confirm our hypothesis, pterocarine ( 2 ) and its close regioisomer 3 were next synthesized following the same synthetic strategy (Scheme 3).…”

mentioning

confidence: 55%

“…The spectroscopic data of our synthetic pterocarine ( 2 ) were identical with those of the originally reported engelhardione 1 as well as natural and synthetic pterocarine. 9, 21 Moreover, on the basis of these spectra, interestingly, we noted that minor structural changes in the substitution patterns at the two aromatic rings result in dramatic differences in their respective NMR spectra. Most notably, for meta and para connected pterocarine ( 2 ) and regioisomer 3 , high-field shifts of H-2′ ( δ = 5.59 ppm, d, J = 1.7 Hz) of 2 (Fig.…”

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confidence: 74%

“…There are basically three different synthetic strategies to construct a macrocyclic diarylheptanoid bearing a diphenyl ether skeleton: (i) the dianion chemistry of methyl acetoacetate and the S N Ar reaction for the diaryl ether formation reported by the Zhu group; 6, 7 (ii) the modified Ullmann reaction and the Wittig reaction reported by the Nógrádi group; 13 and, (iii) the classical Ullmann coupling using a Cu (II) catalyst and aldol condensation reported by the Natarajan 8 and Jahng 9, 10 groups. We chose to adapt the scheme of Jahng et al .…”

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confidence: 99%

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Total synthesis and structural revision of engelhardione

Shen

Sun

2011

Tetrahedron Letters

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The total synthesis of the macrocyclic natural product engelhardione is reported. This effort led to the structural revision of the published structure of engelhardione to that of pterocarine. The revision reflects the change of the substitution pattern of one phenyl ether ring from the meta to the para position. To confirm, pterocarine (2) and its close regioisomer 3 were subsequently synthesized for comparison. Moreover, to the best of our knowledge, our synthesis of 1 represents the first example of a 14-membered macrocyclic diarylheptanoid with a meta-meta substitution pattern at the diphenyl ether moiety.

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confidence: 55%

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confidence: 74%

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confidence: 99%

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Total synthesis and structural revision of engelhardione

Shen

Sun

2011

Tetrahedron Letters

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“…The same reaction sequence was applied to the synthesis of galeon and pterocarine [173]. The catalytic reduction of the double bond of 99c afforded 97b .…”

Section: Total Synthesis Of Biphenyl Diarylheptanoidsmentioning

confidence: 99%

Recent Studies on Cyclic 1,7-Diarylheptanoids: Their Isolation, Structures, Biological Activities, and Chemical Synthesis

Jahng

Park

2018

Molecules

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Diarylheptanoids are a family of plant secondary metabolites with a 7 carbon skeleton possessing two phenyl rings at the 1- and 7-positions. They can be subdivided into acyclic and cyclic diarylheptanoids where the latter are further divided into meta,meta-bridged biphenyls ([7.0]metacyclophanes) and meta,para-bridged diphenyl ether heptanoids (oxa[7.1]metapara-cyclophanes). Since the isolation of curcumin from the rhizomes of turmeric (Curcuma longa) in 1815 which was named curcumin, a variety of diarylheptanoids have been isolated from a number of plant families such as Aceraceae, Actinidiaceae, Betulaceae, Burseraceae, Casuarinaceae, Juglandaceae, Leguminosae, Myricaceae, and Zingiberaceae. Earlier studies on these diarylheptanoids have been summarized on several occasions, of which the main themes only focus on isolation, structure elucidation, and the biological properties of linear types. Only a few have covered cyclic diarylheptanoids and their chemical synthesis has been covered lastly by Zhu et al. in 2000. The present paper has, therefore, covered recent progress in cyclic diarylheptanoids focusing on the isolation, structural and biological features, and chemical synthesis.

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“…The use of classical Ullmann conditions for the formation of the cyclophane skeleton proved to be very efficient in the preparation of galeon ( 11) by Jahng et al (Scheme 5b). 162,163 The copper oxide promoted ring closure of 54 yielded O-benzyl galeon (55) in 52% yield. O-Debenzylation under hydrogenolytic conditions furnished galeon (11).…”

Section: Strain In Cyclophane Natural Productsmentioning

confidence: 99%

Strained cyclophane natural products: Macrocyclization at its limits

2012

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Cyclophane natural products comprise an intriguing class of structurally diverse compounds. As inherent for all cyclic compounds regardless of their origin, macrocyclization is naturally the most decisive step, which defines the overall efficiency of the synthetic pathway. Especially in small cyclophane molecules, this key step constitutes an even greater challenge. Due to the strain imparted by the macrocyclic system, free rotation of the benzene ring(s) is often restricted depending on both the constitution of the tether and the aromatic portions. Not surprisingly, the synthesis of natural cyclophanes with their often outstanding pharmaceutical activities and the inherent issues associated with their preparation has attracted much attention among the synthetic community. In particular, it stimulated the development of new strategies for the ring-closing step, as often otherwise well established and robust reactions fail to perform effectively. In this review, we describe the challenges synthetic chemists are facing during the synthesis of this small, but structurally and biologically fascinating class of natural products, concentrating on the representatives exhibiting configurational stability. The main focus will be on the different concepts for the installation of the macrocyclic system, in most cases the central problem in assembling these extremely rigid molecules.

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First Total Synthesis of Cytotoxic Diarylheptanoids, Galeon, and Pterocarine

Cited by 13 publications

References 33 publications

Total synthesis and structural revision of engelhardione

Total synthesis and structural revision of engelhardione

Recent Studies on Cyclic 1,7-Diarylheptanoids: Their Isolation, Structures, Biological Activities, and Chemical Synthesis

Strained cyclophane natural products: Macrocyclization at its limits

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