- Enantiocomplementary Epoxidation Reactions Catalyzed by an Engineered Cofactor-Independent Non-natural Peroxygenase
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Peroxygenases are heme-dependent enzymes that use peroxide-borne oxygen to catalyze a wide range of oxyfunctionalization reactions. Herein, we report the engineering of an unusual cofactor-independent peroxygenase based on a promiscuous tautomerase that accepts different hydroperoxides (t-BuOOH and H2O2) to accomplish enantiocomplementary epoxidations of various α,β-unsaturated aldehydes (citral and substituted cinnamaldehydes), providing access to both enantiomers of the corresponding α,β-epoxy-aldehydes. High conversions (up to 98 %), high enantioselectivity (up to 98 % ee), and good product yields (50–80 %) were achieved. The reactions likely proceed via a reactive enzyme-bound iminium ion intermediate, allowing tweaking of the enzyme's activity and selectivity by protein engineering. Our results underscore the potential of catalytic promiscuity for the engineering of new cofactor-independent oxidative enzymes.
- Crotti, Michele,Kataja, Kim M.,Poelarends, Gerrit J.,Saravanan, Thangavelu,Xu, Guangcai
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supporting information
p. 10374 - 10378
(2020/04/23)
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- Asymmetric epoxidation of α,β-unsaturated aldehydes catalyzed by a spiro-pyrrolidine-derived organocatalyst
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The asymmetric epoxidation of α,β-unsaturated aldehydes, catalyzed by a spiro-pyrrolidine (SPD)-derived organocatalyst, has been accomplished with good diastereoselectivities (up to dr >20:1) and with high to excellent enantioselectivities (up to 99% ee).
- Xu, Ming-Hui,Tu, Yong-Qiang,Tian, Jin-Miao,Zhang, Fu-Min,Wang, Shao-Hua,Zhang, Shi-Heng,Zhang, Xiao-Ming
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p. 294 - 300
(2017/03/01)
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- Asymmetric epoxidation of α,β-unsaturated aldehydes in aqueous media catalyzed by resin-supported peptide-containing unnatural amino acids
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The enantio- and diastereoselective epoxidation of α,β- unsaturated aldehydes in aqueous media was realized using a resin-supported peptide catalyst. Introducing the hydrophobic and bulky unnatural amino acid 3-(1-pyrenyl)alanine into the peptide sequence was effective for enhancing the reaction rate and enantioselectivity.
- Akagawa, Kengo,Kudo, Kazuaki
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experimental part
p. 843 - 847
(2011/06/11)
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- Stereoselective synthesis of (2S,3R)- and (2R,3S)-iodoreboxetine; Potential SPECT imaging agents for the noradrenaline transporter
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With the aim of developing a new SPECT imaging agent for the noradrenaline transporter, a twelve-step stereoselective synthesis of iodinated analogues of (2S,3R)- and (2R,3S)-reboxetine has been achieved from 4-bromobenzaldehyde. The key steps involve a S
- Jobson, Nicola K.,Spike, Rosemary,Crawford, Andrew R.,Dewar, Deborah,Pimlott, Sally L.,Sutherland, Andrew
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experimental part
p. 2369 - 2376
(2009/02/02)
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- Amine-catalyzed asymmetric epoxidation of α,β-unsaturated aldehydes
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The direct organocatalytic enantioselective epoxidation of α,β-unsaturated aldehydes with different peroxides is presented. Proline, chiral pyrrolidine derivatives, and amino acid-derived imidazolidinones catalyze the asymmetric epoxidation of α,β-unsatur
- Zhao, Gui-Ling,Ibrahem, Ismail,Sunden, Henrik,Cordova, Armando
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p. 1210 - 1224
(2008/09/17)
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- Organocatalytic asymmetric synthesis of 1,2,3-prim,sec,sec-triols
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A tandem organocatalytic asymmetric synthesis of 1,2,3-triols using a,b-unsaturated aldehydes as the substrates and hydrogen peroxide as the oxidant is presented. The reaction can also be applied to the asymmetric synthesis of 3-chloro-1,2-propandiols. Georg Thieme Verlag Stuttgart.
- Zhao, Gui-Ling,Dziedzic, Pawel,Ibrahem, Ismail,Córdova, Armando
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p. 3521 - 3524
(2007/10/03)
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