Science of Synthesis

Faber, K.; Hall, M., Science of Synthesis: Biocatalysis in Organic Synthesis, (2015) 2, 239.

The use of a recycling system with cells coexpressing the ene-reductase and the recycling enzyme can be combined with additional biocatalytic step(s), as shown in the synthesis of methyl 3-oxocyclohexanecarboxylate (‌30‌) (‌Scheme 17‌). The reaction starts with the P450-catalyzed regioselective oxidative C—H activation of methyl cyclohex-1-enecarboxylate (‌29‌), which leads over two steps to the α,β-unsaturated γ-oxo ester. The latter is subsequently reduced by a YqjM mutant to methyl 3-oxocyclohexanecarboxylate (‌30‌). Three hydride equivalents are required for the overall sequence, which are provided by the combination of NADP+/glucose with glucose dehydrogenase (GDH). An engineered E. coli host strain harboring both GDH and YqjM genes inserted in the genome was used, while the gene coding for P450-BM3 was inserted in a plasmid in the same host, thus eliminating the requirement for external biocatalyst sources.[‌86‌]

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‌Meeeeeeeeee 88‌

e Meeeeee eeeeeeeeee ee eee eeeeeee eeeeeeee eeee eeeeee eeeeeeee-8-eeeeeeeeeeeeee (‌88‌).

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‌Meeeee 88‌ Meeeeeeee ee (M)-Meeeeeeee eeeee Meeeeeeeee Meeeeeeeee Meeee Meeeeeeeeee M. eeeeee Meeee[‌88‌]

Meeee eeeeeeee eeeeeee M. eeee eeeee eeeeeeeeeeee 8-eeeeeeeeeeee eeeeeeeee eeee Meeeeeeeeeee ee. MM eee MMM eeee Meeeeeee eeeeeeee eee eee eeeeeeeee ee (M)-8-eeeeeeeeeeeeeee eeee (‌88‌) eeee 8-eeeeeeeeeeeee eeee (‌88‌) (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeee ee (M)-8-Meeeeeeeeeeeeee Meee Meeee Meeeeeeeeee M. eeee Meeee Meeeeeeeeeee 8-Meeeeeeeeeee Meeeeeeee eee Meeeeee Meeeeeeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeee 8-Meeeeeeeeeeeeeeeeeeeeeeee (‌88‌):[‌88‌]

Meeeeeeee eeee eeeeee, eee eeeeeee ee MMM888 eeeee eeeeeeeeeeee M888-MM8 eee MeeM eeeeeee eeeeeeee eeee MMM (88 eM) eee eeeeeeeeeee ee 8888 eee eee 8 eee ee 8 °M. Mee eeee eeeeee eee eeeeeeeeeee ee eeeeeeeee eeeeee (888 eM, eM 8.8; 8 eM) eeeeeeeeee eeeeeee (888 eM). Meeeee eeeeeeee-8-eeeeeeeeeeeeee (‌88‌; 8.8 eM) eee eeeee eee eee eeeeeee eee eeeeeeeee ee 88 °M eeee eeee eeeeeeeee eee 8 e eee eeee eeeeeeeee eeee MeMMe.

(M)-8,8,8-Meeeeeeeeeeeeeeeeeee-8,8-eeeee (‌88‌):[‌88‌]

Mee eeeee (888 ee) ee eeeeeeeeeee M. eeeeee eeee eeeee ee e eeee ee MMMM (888 eM, 88 µM) eee eeeeeeeee ee e eeeeeee ee MeMM (8.888 eM, 8.888 e, 8.88 eeee) eee 8,8,8-eeeeeeeeeeeeeeeee-8-eee-8,8-eeeee (‌88‌; 8.888 eM, 8.888 e, 8.88 eeee). Mee eeeeeeee eee eeeeeeeee ee 88 °M eee 8888 eee eee 88 e. Meeeeeee eeee eeeeeeeeeeeeee eeeee eee eeeeeeeeeee ee eeeeee eee eeeee. Mee eeeeeee eeeee eee eeeeeee eeee MeMMe eee eeeeeeeee ee MM eeeeeeee.

(M)-8-Meeeeeeeeeeeeee Meee (‌88‌):[‌88‌]

Me eee eeeeeee (88 eM) eeeeeeeeee eeeeeeeee 8-eeeeeeeeeeeeee (888 eM), eeeeeee (888 eM), eee MMMM+ (8 eM) eeee eeeee eeeeeeeeeee M. eeee eeeee (88.8 ee/eM, eee eeeeee) eeeeeeeeeeee 8-eeeeeeeeeeee eeeeeeeee eeee Meeeeeeeeeee ee. MM (8888 M) eee MMM eeee Meeeeeee eeeeeeee (8888 M). Mee eeeeeeee eee eeeeeee eee ee 88 °M eee 88 e eee eee eM eee eeeeeeee ee 8.8–8 eeee MMM (8 M) eeeeee eee eeeeeeee.

References