Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts, USA.
Nat Chem Biol. 2017 Aug;13(8):916-921. doi: 10.1038/nchembio.2421. Epub 2017 Jun 26.
Alkylation of aromatic rings with alkyl halides is an important transformation in organic synthesis, yet an enzymatic equivalent is unknown. Here, we report that cylindrocyclophane biosynthesis in Cylindrospermum licheniforme ATCC 29412 involves chlorination of an unactivated carbon center by a novel halogenase, followed by a previously uncharacterized enzymatic dimerization reaction featuring sequential, stereospecific alkylations of resorcinol aromatic rings. Discovery of the enzymatic machinery underlying this unique biosynthetic carbon-carbon bond formation has implications for biocatalysis and metabolic engineering.
芳环的烷基化反应是有机合成中的重要转化反应，但目前尚缺乏酶法等价物。本文报道了节旋藻 Cylindrospermum licheniforme ATCC 29412 中环柱胞苷生物合成涉及一种新型卤化酶对未活化的碳中心进行氯化，随后是一个先前未被表征的酶二聚化反应，其特征是对间苯二酚芳环进行连续、立体特异性的烷基化。该独特生物合成碳-碳键形成的酶促机制的发现对生物催化和代谢工程具有重要意义。
