Abstract
An account is given of the author’s several approaches to the synthesis of the parent chromophore of phytochrome (1 ), a protein-bound linear tetrapyrrole derivative that controls photomorphogenesis in higher plants. These studies culminated in enantioselective syntheses of both (2R )- and (2S )-phytochromobilin (4 ), as well as several 13 C-labeled derivatives designed to probe the site of Z ,E -isomerization during photoexcitation. When reacted in vitro, synthetic 2R -4 and recombinant-derived phytochrome apoprotein N -C produced a protein-bound chromophore with identical difference spectra to naturally occurring 1 .
1 Introduction and Background
2 Early Interests
3 The Azomethine Imine Strategy to Rings A and B:
4 The Sigmatropic Rearrangement Strategy: First Success
5 Regrouping with Pd Chemistry
6 Constructing the C,D-Ring Pyrromethenone of Phytochrome
7 Instability Issues: The ‘BC + D + A’ Strategy
8 Enantioselective Syntheses of (R )- and (S )-Phytochromobilin
9 Probing the Site of Pr Photoisomerization
Key words
phytochrome - pyrroles - lactams - alkynes - palladium
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