2017
DOI: 10.1021/jacs.7b00768
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Highly Diastereo- and Enantioselective Synthesis of Trifluoromethyl-Substituted Cyclopropanes via Myoglobin-Catalyzed Transfer of Trifluoromethylcarbene

Abstract: We report on an efficient strategy for the asymmetric synthesis of trifluoromethyl-substituted cyclopropanes by means of myoglobin-catalyzed olefin cyclopropanation reactions in the presence of 2-diazo-1,1,1-trifluoroethane (CF3CHN2) as the carbene donor. These transformations were realized using a two-compartment setup in which ex situ generated gaseous CF3CHN2 is processed by engineered myoglobin catalysts expressed in bacterial cells. This approach was successfully applied to afford a variety of trans-1-tri… Show more

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Cited by 183 publications
(126 citation statements)
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“…In another recent report, Tinoco et al introduced a two-compartment, chemobiocatalytic strategy for realizing olefin cyclopropanation reactions in the presence of 2-diazo-1,1,1-trifluoroethane (CF 3 CHN 2 ) as the carbene source. This transformation yields trifluoromethyl-substituted cyclopropanes, which are valuable building blocks for medicinal chemistry [28•]. In this system, gaseous CF 3 CHN 2 was generated ex situ and subsequently utilized by whole-cell catalysts expressing engineered Mb cyclopropanation variants.…”
Section: New Carbene Transfer Reactions Catalyzed By Engineered Heme mentioning
confidence: 99%
“…In another recent report, Tinoco et al introduced a two-compartment, chemobiocatalytic strategy for realizing olefin cyclopropanation reactions in the presence of 2-diazo-1,1,1-trifluoroethane (CF 3 CHN 2 ) as the carbene source. This transformation yields trifluoromethyl-substituted cyclopropanes, which are valuable building blocks for medicinal chemistry [28•]. In this system, gaseous CF 3 CHN 2 was generated ex situ and subsequently utilized by whole-cell catalysts expressing engineered Mb cyclopropanation variants.…”
Section: New Carbene Transfer Reactions Catalyzed By Engineered Heme mentioning
confidence: 99%
“…Similar observations have been reported for other protein-based carbene transfer reaction systems. 7,34 Analysis of colony-forming units shows that in vivo organoborane production does not dramatically reduce the viability of the E. coli (Extended Data Fig. 3).…”
mentioning
confidence: 99%
“…Yet only a subset of these engineered enzymes can function in living systems 47 . Finding enzymatic pathways that forge chemical bonds not found in biology is particularly difficult in the cellular environment, as this hinges on the discovery not only of new enzyme activities but also reagents that are simultaneously sufficiently reactive for the desired transformation and stable in vivo .…”
mentioning
confidence: 99%
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“…Engineered heme proteins such as cytochrome P450 enzymes, myoglobin, and cyctochrome C have emerged as excellent catalysts for new‐to‐nature reactions,1, 2 including carbene‐transfer reactions such as cyclopropanations,3, 4, 5, 6, 7 olefinations, and8, 9 N−H,10, 11 Si−H,12 and B−H insertion reactions 13. These enzymes have proven amenable to optimization by both genetic methods and co‐factor replacement 14, 15, 16, 17, 18, 19, 20.…”
mentioning
confidence: 99%