Synthesis of porphobilinogen via a novel ozonide cleavage reaction |
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Authors: | Jacobi P A Li Y |
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Affiliation: | Contribution from the Burke Chemical Laboratory, Dartmouth College, Hanover, New Hampshire 03755. |
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Abstract: | Porphobilinogen lactam methyl ester (3a) has been prepared in seven steps, and approximately 20-30% overall yield, beginning with furfurylamine (4a).(24) Hydrolysis of 3a following the literature procedure then gave porphobilinogen (1). A key intermediate in our synthesis of 3a is the 7-oxonorbornene derivative 7a, which was derived from 4a utilizing a tandem Johnson ortho ester Claisen rearrangement followed by intramolecular Diels-Alder cyclization (five steps, 55-65%).(24) Interesting steric accelerating effects were observed in this sequence. Conversion of 7a to 3a was then accomplished employing a novel ozonide cleavage/oxidation reaction, which generated tetrahydrofurans 16a, 32, and 33 in the proper oxidation state for direct aminolysis to pyrrole 3a. A mechanism is proposed for the ozonide cleavage/oxidation that accounts for the observed stereoselectivity of this step. |
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