Methyl homodaphniphyllate

Methyl homodaphniphyllate
Skeletal structure of a methyl homodaphniphyllate molecule
Skeletal structure of (+)-methyl homodaphniphyllate
Names
IUPAC name
methyl 3-[(1S,2R,3S,7R,10S,13S,14R)-1-methyl-14-propan-2-yl-12-azapentacyclo[8.6.0.02,13.03,7.07,12]hexadecan-2-yl]propanoate
Other names
  • (+)-Homodaphniphyllic acid methyl
  • Methyl homodaphniphyllate acid
  • Daphnan-23-oic acid methyl ester
Identifiers
3D model (JSmol)
  • InChI=1S/C23H37NO2/c1-15(2)17-8-11-21(3)16-7-12-22-10-5-6-18(22)23(21,13-9-19(25)26-4)20(17)24(22)14-16/h15-18,20H,5-14H2,1-4H3/t16-,17-,18-,20+,21+,22-,23+/m1/s1
    Key: NTGCSTZYSQEIFW-KRCCOEDOSA-N
  • CC(C)[C@H]1CC[C@]2([C@@H]3CC[C@]45CCC[C@H]4[C@]2([C@H]1N5C3)CCC(=O)OC)C
Properties
C23H37NO2
Molar mass 359.554 g·mol−1
Melting point 233–234 °C (451–453 °F; 506–507 K)[1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Methyl homodaphniphyllate is a polycyclic molecule belonging to the substance class terpenoid-alkaloids, of which it is the subtype Daphniphyllum-alkaloid, a type of triterpenoid-alkaloid.[2] It is found in the fruits of the shrub Daphniphyllum macropodum.[3] As of yet the effects and biological purpose of this molecule are unknown. However, related molecules in the Daphniphyllum-Alkaloid class show cytotoxic behavior against multiple human cancer cell lines.[4]

Methyl homodaphniphyllate contains a 2-azabicyclo[3.3.1.]nonane system, characteristic of the Daphniphyllum-alkaloids.[5] Of the Daphniphyllum-alkaloids it has the Daphniphylline skeletal structure due to the identical pentacyclic nucleus but differing C-14 substituents.[6] The C-14 substituent on methyl homodaphniphyllate is methyl acetate. This molecule is chiral and the carbon connecting the polycylic ring structure to the substituent arm with methyl acetate is the chiral center. The (+) form rotates clockwise in polarized light. It is possible that methyl homodaphniphyllate is an intermediate between Daphniphylline and other Daphniphyllum-alkaloids in biosynthesis.[7]

History

The first total synthesis of (+)-methyl homodaphniphyllate was performed by Clayton H. Heathcock and his team in 1986 and involves several synthetic steps characterized by repeated ring-closing reactions, ultimately yielding a complex polycyclic alkaloid.[8] Heathcock and others have further researched the synthesis of this molecule to explore the 2-azadiene Diels-Alder cyclization.[9]

References

  1. ↑ Toda, M.; Niwa, H.; Irikawa, H.; Hirata, Y. (January 1, 1974). "The Alkaloids from the Fruits of the Plant Daphniphyllaceae". Tettrahedron. 30 (16): 2683-2688. doi:10.1016/s0040-4020(01)97429-0.
  2. ↑ Cherney, Emily C.; Baran, Phil S. (2011-03-24). "Terpenoid-Alkaloids: Their Biosynthetic Twist of Fate and Total Synthesis". Israel Journal of Chemistry. 51 (3–4): 391–405. doi:10.1002/ijch.201100005. ISSN 0021-2148. PMC 4508874. PMID 26207071.
  3. ↑ Toda, M.; Niwa, H.; Irikawa, H.; Hirata, Y.; Yamamura, S. (1974). "The alkaloids from the fruits of the plant Daphniphyllaceae". Tetrahedron. 30 (16): 2683–2688. doi:10.1016/S0040-4020(01)97429-0.
  4. ↑ Lu, Yunyang; Gao, Kai; Wang, Xiaoyang; Zhang, Wei; Ma, Ning; Tang, Haifeng (2014-03-10). "Five New Alkaloids from the Stem Bark of Daphniphyllum macropodum". Molecules. 19 (3): 3055–3067. doi:10.3390/molecules19033055. ISSN 1420-3049. PMC 6271962. PMID 24619303.
  5. ↑ Vasil, I. K.; Constabel, F.; Bogorad, Lawrence; Schell, Jozef Stephaan (1984). Cell culture and somatic cell genetics of plants. Orlando, Fla: Academic Press. ISBN 978-0-12-715001-7.
  6. ↑ Wu, Haifeng; Zhang, Xiaopo; Ding, Lisheng; Chen, Shilin; Yang, Junshan; Xu, Xudong (2013-11-08). "Daphniphyllum Alkaloids: Recent Findings on Chemistry and Pharmacology". Planta Medica. 79 (17): 1589–1598. Bibcode:2013PlMed..79.1589W. doi:10.1055/s-0033-1351024. ISSN 0032-0943. PMID 24214836.
  7. ↑ Toda, Masaaki; Yamamura, Shosuke; Hirata, Yoshimasa (January 1969). "Isolation and the structure of methyl homodaphniphyllate, a plausible intermediate between daphniphylline and yuzurimine". Tetrahedron Letters. 10 (30): 2585–2586. doi:10.1016/S0040-4039(01)88574-9.
  8. ↑ Heatcock, Clayton H.; Davidsen, Steven K.; Mills, Sander; Sanner, Mark A. (1986). "Total Synthesis of (+)-Methyl Homodaphniphyllate". Journal of the American Chemical Society. 108 (16): 5650–5651. Bibcode:1986JAChS.108.5650H. doi:10.1021/ja00278a061.
  9. ↑ Wallace, Grier A.; Heathcock, Clayton H. (2001). "Further Studies of the Daphniphyllum Alkaloid Polycyclization Cascade". The Journal of Organic Chemistry. 66 (2): 450–454. doi:10.1021/jo001145r. PMID 11429813.
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