초록
<P><SMALL>l</SMALL>-Tyrosine derivatives were obtained in >97% ee via a biocatalytic one-pot two-step cascade using substituted benzenes, pyruvate, and NH<SUB>3</SUB> as starting materials. In the first step, monosubstituted arenes were regioselectively hydroxylated in the <I>o</I>-position by monooxygenase P450 BM3 (using O<SUB>2</SUB> as oxidant with NADPH-recycling) to yield the corresponding phenols, which subsequently underwent C–C coupling and simultaneous asymmetric amination with pyruvate and NH<SUB>3</SUB> using tyrosine phenol lyase to furnish <SMALL>l</SMALL>-DOPA surrogates in up to 5.2 g L<SUP>–1</SUP>. Instead of analytically pure arenes, crude aromatic gasoline blends containing toluene were used to yield 3-methyl-<SMALL>l</SMALL>-tyrosine in excellent yield (2 g L<SUP>–1</SUP>) and >97% ee.</P><P><B>Graphic Abstract</B><BR><IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/accacs/2015/accacs.2015.5.issue-12/acscatal.5b02129/production/images/medium/cs-2015-021299_0004.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/cs5b02129'>ACS Electronic Supporting Info</A></P>