Biotransformations of Arenes

Design and Synthesis of C-1 Methoxycarbonyl Derivative of Narciclasine and Its Biological Activity

“…The more elaborate synthesis of the C-ring coupling precursor, which contains all the necessary chiral centers of the final product, begins with the enzymatic dihydroxylation of ortho-dibromobenzene (13, Scheme 3). This is accomplished by a whole-cell fermentation process [20] with a recombinant strain of E. coli JM109 (pDTG601A [21]) that over-expresses toluene dioxygenase and was successfully used for the oxidative de-aromatization of various aromatic substrates [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] employed in the synthesis of natural products. Once dibromodiene diol 12 was obtained, it was subjected to acetonide protection and a nitroso Diels-Alder reaction in a one-pot procedure to form the bicyclic oxazine 21.…”

Quantitative 1H-NMR analysis reveals steric and electronic effects on the substrate specificity of benzoate dioxygenase in Ralstonia eutropha B9

“…The dihydroxylation reaction is often regio- and stereoselective, leading to the formation of chiral dihydrodiols. This has given rise to sustained interest in these metabolites as building blocks in the synthesis of important small molecules (Hudlicky, 2018 ; Lewis, 2015 ). The ortho,meta cis -dihydrodiols ( 2 ) are typically derived from toluene (TDO), naphthalene (NDO), and biphenyl dioxygenases (BPDOs) expressed in whole cells (Wackett, 2002 ).…”

“…By comparison, the ipso,ortho cis- dihydrodiols ( 3 ) have been applied far less frequently (Hudlicky, 2018 ; Lewis, 2014 ). These metabolites can be accessed through the 1,2-dihydroxylation of benzoic acids using toluate (TADO) and benzoate dioxygenases (BZDOs) (Lewis, 2015 ; Whited et al, 1986 ). The most widely applied system for production of ipso,ortho cis -dihydrodiols is Ralstonia eutropha B9 (formerly Alcaligenes eutrophus , now Cupriavidus necator ) whole cells expressing BZDO (Reiner & Hegeman, 1971 ).…”