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Literature DB >> 21505494

Stereoselective C-C bond formation catalysed by engineered carboxymethylproline synthases.

Refaat B Hamed¹, J Ruben Gomez-Castellanos, Armin Thalhammer, Daniel Harding, Christian Ducho, Timothy D W Claridge, Christopher J Schofield.

Abstract

The reaction of enol(ate)s with electrophiles is used extensively in organic synthesis for stereoselective C-C bond formation. Protein-based catalysts have had comparatively limited application for the stereoselective formation of C-C bonds of choice via enolate chemistry. We describe protein engineering studies on 5-carboxymethylproline synthases, members of the crotonase superfamily, aimed at enabling stereoselective C-C bond formation leading to N-heterocycles via control of trisubstituted enolate intermediates. Active site substitutions, including at the oxyanion binding site, enable the production of substituted N-heterocycles in high diastereomeric excesses via stereocontrolled enolate formation and reaction. The results reveal the potential of the ubiquitous crotonase superfamily as adaptable catalysts for the control of enolate chemistry.

Entities: Chemical

Mesh：

Substances：

Year: 2011 PMID： 21505494 DOI： 10.1038/nchem.1011

Source DB: PubMed Journal: Nat Chem ISSN： 1755-4330 Impact factor: 24.427

20 in total

1. The crotonase superfamily: divergently related enzymes that catalyze different reactions involving acyl coenzyme a thioesters.

Authors: H M Holden; M M Benning; T Haller; J A Gerlt
Journal: Acc Chem Res Date: 2001-02 Impact factor: 22.384

2. The desymmetrization of bicyclic beta -diketones by an enzymatic retro-Claisen reaction. A new reaction of the crotonase superfamily.

Authors: G Grogan; G A Roberts; D Bougioukou; N J Turner; S L Flitsch
Journal: J Biol Chem Date: 2001-01-16 Impact factor: 5.157

Review 3. Directed evolution of enzymes and biosynthetic pathways.

Authors: Tyler W Johannes; Huimin Zhao
Journal: Curr Opin Microbiol Date: 2006-04-18 Impact factor: 7.934

4. Structural basis for cofactor-independent dioxygenation in vancomycin biosynthesis.

Authors: Paul F Widboom; Elisha N Fielding; Ye Liu; Steven D Bruner
Journal: Nature Date: 2007-05-17 Impact factor: 49.962

5. Carboxymethylproline synthase from Pectobacterium carotorova: a multifaceted member of the crotonase superfamily.

Authors: Barbara Gerratana; Samantha O Arnett; Anthony Stapon; Craig A Townsend
Journal: Biochemistry Date: 2004-12-21 Impact factor: 3.162

6. Interchange of catalytic activity within the 2-enoyl-coenzyme A hydratase/isomerase superfamily based on a common active site template.

Authors: H Xiang; L Luo; K L Taylor; D Dunaway-Mariano
Journal: Biochemistry Date: 1999-06-15 Impact factor: 3.162

7. Mutation of Lys242 allows Delta3-Delta2-enoyl-CoA isomerase to acquire enoyl-CoA hydratase activity.

Authors: Wenhua Yu; Xiusheng Chu; Guisheng Deng; Xiaojun Liu; Gong Chen; Ding Li
Journal: Biochim Biophys Acta Date: 2006-08-03

8. Carboxylation mechanism and stereochemistry of crotonyl-CoA carboxylase/reductase, a carboxylating enoyl-thioester reductase.

Authors: Tobias J Erb; Volker Brecht; Georg Fuchs; Michael Müller; Birgit E Alber
Journal: Proc Natl Acad Sci U S A Date: 2009-05-20 Impact factor: 11.205

9. Carboxymethylproline synthase (CarB), an unusual carbon-carbon bond-forming enzyme of the crotonase superfamily involved in carbapenem biosynthesis.

Authors: Mark C Sleeman; Christopher J Schofield
Journal: J Biol Chem Date: 2003-11-18 Impact factor: 5.157

10. Synthesis of C5-dicarboxylic acids from C2-units involving crotonyl-CoA carboxylase/reductase: the ethylmalonyl-CoA pathway.

Authors: Tobias J Erb; Ivan A Berg; Volker Brecht; Michael Müller; Georg Fuchs; Birgit E Alber
Journal: Proc Natl Acad Sci U S A Date: 2007-06-04 Impact factor: 11.205

5 in total

Stereoselective C-C bond formation catalysed by engineered carboxymethylproline synthases.

1. The crotonase superfamily: divergently related enzymes that catalyze different reactions involving acyl coenzyme a thioesters.

2. The desymmetrization of bicyclic beta -diketones by an enzymatic retro-Claisen reaction. A new reaction of the crotonase superfamily.

Review 3. Directed evolution of enzymes and biosynthetic pathways.

4. Structural basis for cofactor-independent dioxygenation in vancomycin biosynthesis.

5. Carboxymethylproline synthase from Pectobacterium carotorova: a multifaceted member of the crotonase superfamily.

6. Interchange of catalytic activity within the 2-enoyl-coenzyme A hydratase/isomerase superfamily based on a common active site template.

7. Mutation of Lys242 allows Delta3-Delta2-enoyl-CoA isomerase to acquire enoyl-CoA hydratase activity.

8. Carboxylation mechanism and stereochemistry of crotonyl-CoA carboxylase/reductase, a carboxylating enoyl-thioester reductase.

9. Carboxymethylproline synthase (CarB), an unusual carbon-carbon bond-forming enzyme of the crotonase superfamily involved in carbapenem biosynthesis.

10. Synthesis of C5-dicarboxylic acids from C2-units involving crotonyl-CoA carboxylase/reductase: the ethylmalonyl-CoA pathway.

Review 1. Carboxylases in natural and synthetic microbial pathways.

2. Mechanism of the C5 stereoinversion reaction in the biosynthesis of carbapenem antibiotics.

Review 3. Rational approaches for engineering novel functionalities in carbon-carbon bond forming enzymes.

Review 4. Roles of 2-oxoglutarate oxygenases and isopenicillin N synthase in β-lactam biosynthesis.

5. Biocatalytic production of bicyclic β-lactams with three contiguous chiral centres using engineered crotonases.