Biocatalytic Synthesis of Allylic and Allenyl Sulfides through a Myoglobin-Catalyzed Doyle-Kirmse Reaction.
作者： Vikas Tyagi , Gopeekrishnan Sreenilayam , Priyanka Bajaj , Antonio Tinoco , Rudi Fasan
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摘要: The first example of a biocatalytic [2,3]-sigmatropic rearrangement reaction involving allylic sulfides and diazo reagents (Doyle–Kirmse reaction) is reported. Engineered variants sperm whale myoglobin catalyze this synthetically valuable C−C bond-forming transformation with high efficiency product conversions across variety sulfide substrates (e.g., aryl-, benzyl-, alkyl-substituted sulfides) α-diazo esters. Moreover, the scope myoglobin-mediated could be extended to conversion propargylic give substituted allenes. Active-site mutations proved effective in enhancing catalytic hemoprotein these reactions as well modulating enantioselectivity, resulting identification variant Mb(L29S,H64V,V68F), which capable mediating asymmetric Doyle–Kirmse an enantiomeric excess up 71 %. This work extends toolbox currently available strategies for formation carbon–carbon bonds.
sci-hub.se 参考文章(59)
Poonam Srivastava, Hao Yang, Ken Ellis-Guardiola, Jared C. Lewis, Engineering a dirhodium artificial metalloenzyme for selective olefin cyclopropanation Nature Communications. ,vol. 6, pp. 7789- 7789 ,(2015) , 10.1038/NCOMMS8789
Simone Giovani, Ritesh Singh, Rudi Fasan, Efficient conversion of primary azides to aldehydes catalyzed by active site variants of myoglobin Chemical Science. ,vol. 7, pp. 234- 239 ,(2016) , 10.1039/C5SC02857D
Helle D. Ulrich, Emily Mundorff, Bernard D. Santarsiero, Edward M. Driggers, Raymond C. Stevens, Peter G. Schultz, The interplay between binding energy and catalysis in the evolution of a catalytic antibody Nature. ,vol. 389, pp. 271- 275 ,(1997) , 10.1038/38470
Nicholas J Turner, Directed evolution drives the next generation of biocatalysts Nature Chemical Biology. ,vol. 5, pp. 567- 573 ,(2009) , 10.1038/NCHEMBIO.203
Ming Ma, Lingling Peng, Changkun Li, Xiu Zhang, Jianbo Wang, Highly stereoselective [2,3]-sigmatropic rearrangement of sulfur ylide generated through Cu(I) carbene and sulfides. Journal of the American Chemical Society. ,vol. 127, pp. 15016- 15017 ,(2005) , 10.1021/JA055021D
Paul W. Davies, Sébastien J.-C. Albrecht, Giulio Assanelli, Silver-catalysed Doyle–Kirmse reaction of allyl and propargyl sulfides Organic and Biomolecular Chemistry. ,vol. 7, pp. 1276- 1279 ,(2009) , 10.1039/B822584B
Clemens Mayer, Dennis G. Gillingham, Thomas R. Ward, Donald Hilvert, An artificial metalloenzyme for olefin metathesis. Chemical Communications. ,vol. 47, pp. 12068- 12070 ,(2011) , 10.1039/C1CC15005G
Manfred T. Reetz, Biocatalysis in Organic Chemistry and Biotechnology: Past, Present, and Future Journal of the American Chemical Society. ,vol. 135, pp. 12480- 12496 ,(2013) , 10.1021/JA405051F
Michael S. Holzwarth, Isabel Alt, Bernd Plietker, Catalytic activation of diazo compounds using electron-rich, defined iron complexes for carbene-transfer reactions. Angewandte Chemie. ,vol. 51, pp. 5351- 5354 ,(2012) , 10.1002/ANIE.201201409
U. T. Bornscheuer, G. W. Huisman, R. J. Kazlauskas, S. Lutz, J. C. Moore, K. Robins, Engineering the third wave of biocatalysis Nature. ,vol. 485, pp. 185- 194 ,(2012) , 10.1038/NATURE11117