ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The total synthesis of racemic cis-2,3,181, 182, -tetrahydroprotobiliverdin IXα dimethyl ester (19b), which is identical with the dimethyl ester of rac-4, is described (Scheme 2). Under virtually neutral conditions, in solution, this bile pigment isomerized within a few min to racemic Z-phycocyanobilin dimethyl ester (rac-5b). Likewise, acid-catalyzed allyl rearrangement of 3-vinyl-substituted cis- and trans-2,3-dihydrodipyrrin-1(10H)-ones 11c and 13c, respectively, yielded the corresponding ethylidene derivatives. In this case, however, the E-isomer was formed stereo selectively from both substrates. The above results prove that, if protobiliverdin IXα (2) is transformed enzymatically to its 2,3,181, 182-tetrahydro derivative, the latter would isomerize spontaneously to phycocyanobi-lin. The biosynthesis of bacteriochlorophyll a and b from a common precursor bearing a vinyl group at C(8)may be straightforwardly explained in the same way.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19890720315
