Syntheses of Bile Pigments. Part 16. Synthesis of a vinyl‐substituted 2,3‐Dihydrobilinedione: Possible role of this new class of bile pigments in phycobilin biosynthesis

Gossauer, Albert; Nydegger, Fredy; Benedikt, Eva; Köst, Hans‐Peter

doi:10.1002/hlca.19890720315

Cited by 25 publications

(7 citation statements)

References 42 publications

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“…The existence of the (3Z)-phycobilins may be rationalized by proposing that the 2,3-reductase reaction that forms the reduced pyrrole ring uses, as substrate, a bilin that has a 3-vinyl group and produces, as the immediate product, a 3-vinyl-2,3-dihydrobilin. Gossauer et al 93 have shown that synthetic 3-vinyl-2,3dihydrobilins spontaneously isomerize to (3Z)-3ethylidene-2,3-dihydrobilins. Thus, enzymatic pyrrole reduction of biliverdin or another 3-vinylbilin would initially yield the unstable 3-vinyl-2,3-dihydrobilin, which would nonenzymatically isomerize to the (3Z)-3-ethylidene-2,3-dihydrobilin.…”

Section: B Transformation Of Biliverdin To Phycocyanobilin By Extract...mentioning

confidence: 99%

Biosynthesis of phycobilins

Beale¹

1993

Chem. Rev.

134

136

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Section: B Transformation Of Biliverdin To Phycocyanobilin By Extract...mentioning

confidence: 99%

Biosynthesis of phycobilins

Beale¹

1993

Chem. Rev.

134

136

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“…Further degradation steps will generate a series of nonfluorescent Chl catabolites (NCCs) generally viewed as the final breakdown products of chlorophyll a. However, structural similarities between known NCCs such as Brassica napus-NCC-3 (Mühlecker and Kräutler, 1996), also found in Arabidopsis thaliana (Pružinská et al, 2005), and compounds 1 and 2 suggest that 1 and 2 are tripyrrolic (Gossauer et al, 1989). Since these compounds were isolated from the leaves of Crataegus pinnatifida Bge var.…”

Section: Resultsmentioning

confidence: 99%

The first tripyrrolic chlorophyll catabolites isolated from Crataegus pinnatifida Bge. var. major brown leaves

Zhang

Yang

Stien

2020

Phytochemistry Letters

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“…Compound 13 was then reduced with aluminum amalgam to 14, 8 followed by acid treatment to result in the formation of A/Bring component 15. 9 The transformation of 13 to 15 through the reduced intermediate 14 is of interest in connection with the mostly speculative pathway for the transformation of biliverdin IXa to 1 through "dihydrobiliverdin." 10 On the other hand, we previously reported a novel synthetic method of C/D-ring component of phytochromobilin dimethyl ester utilizing 4-methyl-5-tosyl-3-(2tosylethyl)pyrrolinone.…”

Section: Based On This Strategy We First Prepared the A/b-ring Component (Scheme 2)mentioning

confidence: 99%

Total Synthesis of (±)-Phytochromobilin Starting from Two Pyrrole Derivatives

Kakiuchi

Kinoshita

Inomata

1999

Synlett

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±)-Phytochromobilin was synthesized as an acid form by developing a convenient method for the preparation of A-and Drings starting from a 2-tosylpyrrole derivative, followed by efficient construction of A/B-and C/D-ring components via Wittig-type coupling reaction of 5-tosylpyrrolinones with 2-formylpyrrole, and palladium catalyzed deprotection of allyl esters of propanoic acid side chains at C-8 and C-12.Phytochrome is a chromoprotein concerned in a variety of processes in higher plants such as growth, development, and morphogenesis etc. The chromophore named phytochromobilin (1) is a linear tetrapyrrole derivative and covalently bound to the apoprotein at A-ring. Recent developments in gene technology have made it possible to assemble the chromophores such as phytochromobilin (1) and phycocyanobilin (2), the latter of which is a chromophore of phycocyanin found in algal photosynthetic systems, with the apoproteins obtained by the over-expression of the corresponding cDNA in bacteria and yeast. The photophysical and photochemical properties of wild type phytochrome are quite similar to those of the reconstituted phytochromes. 1On the other hand, though the total syntheses of dimethyl ester derivatives of the chromophores 1 and 2 have been reported by Gossauer and his co-workers, 2 there had been no report regarding the syntheses of their acid forms applicable to assemble with the apoproteins.In 1998, we reported the total synthesis of 2 and its derivatives bearing a photoreactive group at the D-ring in their acid form for the structure/function analysis of phytochrome. 3 Also Gärtner and his co-workers reported the syntheses of 1 and its isomer by the cleavage at C-10 of biliverdin IXa dimethyl ester with the thiobarbiturate anion. 4In this paper, we wish to describe the novel total synthesis of (±)-phytochromobilin (1) in its acid form starting from 4-methyl-3-[2-(tolythio)ethyl]-2-tosylpyrrole (8) as a common precursor of the A-and D-rings and 2-formylpyrrole 11 which is common to the B-and C-rings via our Wittig-type coupling reaction (Scheme 1).Recently we reported a new and efficient construction of the A/B-ring component for the syntheses of phycocyanobilin (2) and its derivatives using 4-(1-methoxyethyl)-3-methyl-5-tosyl-1,5-dihydro-2H-pyrrol-2-one as a precursor of the A-ring and 2-formylpyrrole 11. 3cIf it is possible to construct the A/B-and C/D-rings components of 1 starting from the same building blocks and the same coupling way, respectively, it will provide a much more efficient route for the total synthesis of 1. Based on this strategy, we first prepared the A/B-ring component (Scheme 2).The aldehyde 5, readily available by addition of p-toluenethiol to acrolein (4), was reacted with nitroethane to give nitroalcohol 6, which was acetylated and cyclized utilizing tosylmethyl isocyanide (TosMIC) 5 in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) to afford the pyrrole derivative 8 being regarded as a common precursor of the A-and D-rings. 6 The 5-tosylpyrrolinone 10 was obtained from 8 by ...

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Syntheses of Bile Pigments. Part 16. Synthesis of a vinyl‐substituted 2,3‐Dihydrobilinedione: Possible role of this new class of bile pigments in phycobilin biosynthesis

Cited by 25 publications

References 42 publications

Biosynthesis of phycobilins

Biosynthesis of phycobilins

The first tripyrrolic chlorophyll catabolites isolated from Crataegus pinnatifida Bge. var. major brown leaves

Total Synthesis of (±)-Phytochromobilin Starting from Two Pyrrole Derivatives

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