Fastigiatine, a lycopodium alkaloid with a new ring system

Abstract

. LOCK. Can. J. Chem. 64,943 (1986). Fastigiatine, C19H28N20, is a minor component of the alkaloids of Lycopodium fastigiatum R. Br. collected in New Zealand.Its structure and relative configuration have been resolved by an X-ray analysis of the free base. The pentacyclic ring system of fastigiatine has not been previously observed in the Lycopodium family of alkaloids or elsewhere. A proposal is presented for its derivation from the tetracyclic flabellidane ring system that is widely distributed among Lycopodium species. The mass spectrum and the 13c and 'H nrnr spectra of fastigiatine are discussed.ROBERT V. GERARD, DAVID B. MACLEAN, ROMOLO FAGIANN~, et COLIN J. LOCK. Can. J. Chem. 64, 943 (1986). La fastigiatine, C19H28N20, est un constituant mineur des alcalo'ides du Lycopodium fastigiatine R. Br. rtcoltt en Nouvelle Zlande. On a rtsolu sa structure et sa configuration relative par I'analyse aux rayons-X de la base libre. On n'avait pas encore observt le systtme pentacyclique de la fastigiatine dans la farnille des alcalo~des du Lycopodium ou ailleurs. On propose une mtthode de prtpariition de la fastigiatine h partir du systkme tttracyclique de la flabellidane que I'on retrouve souvent dans les espkes du Lycopodium. On discute du spectre de masse et des spectres rmn du I3c et du 'H de la fastigiatine.[Traduit par la revue]

Total Synthesis of (−)‐Himeradine A

“…The relative configuration at C17 and C10′ was assigned by the NOESY correlations between H17/H10′, H11′/H8′, H11′/H6′, and H11′/H2′. The absolute configuration of the molecule was assigned based on analogy to the structure of fastigiatine …”

“…Ther elative configuration at C17 and C10' was assigned by the NOESY correlations between H17/H10', H11'/H8',H11'/H6',and H11'/H2'.The absolute configuration of the molecule was assigned based on analogy to the structure of fastigiatine. [9] Our approach towards (À)-himeradine Ab uilt on our first-and second-generation syntheses of fastigiatine, [10] and is outlined in Figure 2. Thefastigiatine core would be assembled by at ransannular Mannich reaction from intermediate 3, which was inspired by the proposed biosynthesis.…”

Biomimetic Synthesis of Ornithine/Arginine and Lysine‐Derived Alkaloids: Selected Examples

“…Many achievements in biomimetic synthesis of Nitraria alkaloids have been disclosed by the Koomen group [88] and the Husson group [89]. Representative structures [myrioneurinol (158) and myrobotinol (127)] are presented in Scheme 1.39 [90]; they constitute ideal targets for total synthesis inspired by biosynthetic pathways. More recently, a phytochemical study of Myrioneuron nutans (a species collected in Vietnam from a small genus within the Rubiaceae family) by Bodo and colleagues at the Museum National d'Histoire Naturelle in Paris revealed the presence of a new class of alkaloids that was named ''Myrioneuron alkaloids.''…”

“…Scheme 1.61Biomimetic synthesis of senepodine G and cermizine C.1.5.4.7 Biomimetic Steps in the Total Synthesis of Fastigiatine Fastigiatine (222, Scheme 1.62) was isolated as a minor alkaloid from Lycopodium fastigiatum in 1985 by the MacLean group[127]. The first total synthesis of this complex alkaloid was only accomplished in 2010 by the Shair group (Scheme 1.62)[128].…”

The lycopodium alkaloids

“…H-5 in (32) and (34) shows observable coupling to only one of the H-6's (5 Hz), smaller allylic coupling (1 Hz), and no coupling to H-7. Oxidation of lobscurinol provided the diketone (35) which was named lobscurinine (carbonyl absorption at 1722 cm-' (cyclopentanone) and 1663 cm-' (cyclohexenone)). Lobscurinine was not isolated among the alkaloids of L. obscuruyy~, but its interesting ammonia adduct, obscurinine (36), was present.…”