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Raspailynes, Novel Long‐Chain Acetylenic Enol Ethers of Glycerol from the Marine Sponges Raspailia pumila and Raspailia ramosa
Author(s) -
Guella Graziano,
Mancini Ines,
Pietra Francesco
Publication year - 1987
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19870700417
Subject(s) - chemistry , stereochemistry , double bond , enol , propanediol , glycerol , ether , organic chemistry , catalysis
The sponges Raspailia pumila and ramosa (Demospongiae, Tetractinomorpha, Axinellida) from the North‐East Atlantic are shown to contain a series of novel long‐chain enol ethers of glycerol where the enol ether CC bond is conjugated, in sequence, to both an acetylenic and an olefinic bond. Polar extracts give raspailynes hydroxylated at their (1 Z 5 Z )‐1,5‐alkadien‐3‐ynyl chain, like raspailyne Al ( = (+)‐( S )‐3‐[((1 Z ,5 Z )‐16‐hydroxy‐hexadeca‐1,5‐dien‐3‐ynyl)oxy]‐1,2‐propanediol; (+ 2 ) and isoraspailyne A ( = (+)‐3‐[((1 Z ,5 Z )‐17‐hydroxyocta‐deca‐1,5‐dien‐3‐ynyl)oxy]‐1,2‐[propanediol; (+)‐ 3 ). Less polar extracts give 3 different types of raspailynes not hydroxylated at the chain. Raspailynes of the first type have either the (1 Z ,5 Z )‐configuration in a linear chain such as raspailyne B2 (( = (−)‐( s )‐3‐[((1 Z ,5 Z )‐trideca‐1,5‐dien‐3‐ynyl)oxy]‐1,2‐propanediol; (−)‐ 4 ), raspailyne Bl ( = (−)‐3‐[((1 Z ,5 Z )‐tetradeca‐1,5‐dien‐3‐ynyl)oxy]‐1,2‐propanediol;(−)‐ 5 ), and raspailyne B ( = 3‐[((1 Z ,5 Z )‐pentadeca‐1,5‐dien‐3‐ynyl)oxy]‐1,2‐propanediol; 6 ) or the (1 Z ,5 Z )‐pentadeca‐1,5‐dien‐3‐ynyl)oxy]‐1,2‐propanediol; 6 )or the (1 Z ,5 Z )‐configuration in a chain ending with an isopropyl group, like isoraspailyne Bl ( = 3‐[((1 Z ,5 Z )‐12‐methyltrideca‐1,5‐dien‐3‐ynyl)oxy]‐1,2‐propanediol; 7 ) and isoraspailyne B ( = 3‐[((1 Z ,5 Z )‐13‐methyltetradeca‐1,5‐dien‐3‐ynyl)oxy]‐1,2‐propanediol; 8 ). Raspailynes of the second type have the (1 Z ,5 E )‐configuration, like isoraspailyne Bla ( =3‐[((1 Z ,5 E )‐tetradeca‐1,5‐dien‐3‐ynyl)oxy]‐1,2‐propanediol; 9 ) and isoraspailyne Ba ( = 3‐[((1 Z ,5 E )‐13‐methyltetradeca‐1,5‐dien‐3‐ynyl)oxy]‐1,2‐propanediol; 10 ). Raspailynes of the third type have the (1 E ,5 Z )‐configuration, like isoraspailyne Blb ( = 3‐[((1 E ,5 Z )‐tetradeca‐1,5‐dien‐3‐ynyl)oxy]‐1,2,‐propanediol; 11 ). The ( S )‐configuration for (+)‐ 1 ,((+)‐ 2 , and (−)‐ 4 is derived from chemical correlations.