77341-56-1Relevant academic research and scientific papers
‘Reverse biomimetic’ synthesis ofl-arogenate and its stabilized analogues froml-tyrosine
Boden, Grace,Clayden, Jonathan,Eagling, Louise,Leonard, Daniel J.,Schwarz, Maria,Urruzuno, I?aki,Wailes, J. Steven,Ward, John W.
, p. 11394 - 11398 (2021)
l-Arogenate (also known asl-pretyrosine) is a primary metabolite on a branch of the shikimate biosynthetic pathway to aromatic amino acids. It plays a key role in the synthesis of plant secondary metabolites including alkaloids and the phenylpropanoids that are the key to carbon fixation. Yet understanding the control of arogenate metabolism has been hampered by its extreme instability and the lack of a versatile synthetic route to arogenate and its analogues. We now report a practical synthesis ofl-arogenate in seven steps fromO-benzyll-tyrosine methyl ester in an overall yield of 20%. The synthetic route also delivers the fungal metabolite spiroarogenate, as well as a range of stable saturated and substituted analogues of arogenate. The key step in the synthesis is a carboxylative dearomatization by intramolecular electrophilic capture of tyrosine's phenolic ring using anN-chloroformylimidazolidinone moiety, generating a versatile, functionalizable spirodienone intermediate.
