Examples of Catalytic and Selective Routes for Fluorinated Building Blocks

2014 ◽  
Vol 18 (8) ◽  
pp. 1067-1071 ◽  
Author(s):  
Sylvette Brunet
Keyword(s):  
Building Blocks ◽  
Fluorinated Building Blocks

scholarly journals A fluoride-responsive genetic circuit enables in vivo biofluorination in engineered Pseudomonas putida

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Patricia Calero ◽  
Daniel C. Volke ◽  
Phillip T. Lowe ◽  
Charlotte H. Gotfredsen ◽  
David O’Hagan ◽  
...  
Keyword(s):  
Pseudomonas Putida ◽  
Building Blocks ◽  
T7 Rna Polymerase ◽  
Genetic Circuit ◽  
Gene Circuits ◽  
Fluorinated Building Blocks ◽  
Synthetic Gene Circuits ◽  
Cell Factories ◽  
Synthetic Circuit

Abstract Fluorine is a key element in the synthesis of molecules broadly used in medicine, agriculture and materials. Addition of fluorine to organic structures represents a unique strategy for tuning molecular properties, yet this atom is rarely found in Nature and approaches to integrate fluorometabolites into the biochemistry of living cells are scarce. In this work, synthetic gene circuits for organofluorine biosynthesis are implemented in the platform bacterium Pseudomonas putida. By harnessing fluoride-responsive riboswitches and the orthogonal T7 RNA polymerase, biochemical reactions needed for in vivo biofluorination are wired to the presence of fluoride (i.e. circumventing the need of feeding expensive additives). Biosynthesis of fluoronucleotides and fluorosugars in engineered P. putida is demonstrated with mineral fluoride both as only fluorine source (i.e. substrate of the pathway) and as inducer of the synthetic circuit. This approach expands the chemical landscape of cell factories by providing alternative biosynthetic strategies towards fluorinated building-blocks.

Toward the synthesis of novel fluorinated building blocks: 3,4-difluorothiophene-1,1-dioxide

1999 ◽  
Vol 93 (1) ◽  
pp. 27-31 ◽  
Author(s):  
Ireneusz Nowak ◽  
Lillian M. Rogers ◽  
Robin D. Rogers ◽  
Joseph S. Thrashe
Keyword(s):  
Building Blocks ◽  
Fluorinated Building Blocks

A concise approach to CF3-containing furan-3-ones, (bis)pyrazoles from novel fluorinated building blocks based on 2,3-butanedione

2014 ◽  
Vol 55 (42) ◽  
pp. 5714-5717 ◽  
Author(s):  
Denis N. Bazhin ◽  
Dmitry L. Chizhov ◽  
Gerd-Volker Röschenthaler ◽  
Yulia S. Kudyakova ◽  
Yanina V. Burgart ◽  
...  
Keyword(s):  
Building Blocks ◽  
Fluorinated Building Blocks

ChemInform Abstract: Synthetically Useful C-4 Fluorinated Building Blocks Bearing a Quaternary Stereocenter.

ChemInform ◽  
2010 ◽  
Vol 26 (19) ◽  
pp. no-no
Author(s):  
A. ARNONE ◽  
P. BRAVO ◽  
M. FRIGERIO ◽  
G. SALANI ◽  
F. VIANI
Keyword(s):  
Building Blocks ◽  
Fluorinated Building Blocks ◽  
Quaternary Stereocenter

scholarly journals Biocatalytic asymmetric construction of secondary and tertiary fluorides from β-fluoro-α-ketoacids

2021 ◽  
Author(s):  
Jason Fang ◽  
Laura Turner ◽  
Michelle Chang
Keyword(s):  
Asymmetric Synthesis ◽  
Kinetic Resolution ◽  
Bond Formation ◽  
Aldol Reaction ◽  
Building Blocks ◽  
Critical Element ◽  
Type Ii ◽  
Fluorinated Building Blocks ◽  
Reaction Proceeds ◽  
New Donors

Fluorine is a critical element for the design of bioactive compounds, but its incorporation with high regio- and stereoselectivity using environmentally friendly reagents and catalysts remains an area of development. Stereogenic tertiary fluorides pose a particular synthetic challenge and are thus present in only a few approved pharmaceuticals such as fluticasone, solithromycin, and sofosbuvir. The aldol reaction of fluorinated donors provides an atom-economical approach to asymmetric C-F motifs via C-C bond formation. Here we report that the type II pyruvate aldolase HpcH and engineered mutants thereof are biocatalysts for carboligation of ß-fluoro-α-ketoacids (including fluoropyruvate, ß-fluoro-α-ketobutyrate, and ß-fluoro-α-ketovalerate) with many diverse aldehydes. The reaction proceeds with kinetic resolution in the case of racemic donors. The reactivity of HpcH towards these new donors, which are non-native in both steric and electronic properties, grants access to enantiopure fragments with secondary or tertiary fluoride stereocenters. In addition to representing the first asymmetric synthesis of tertiary fluorides via biocatalytic carboligation, the afforded products could improve the diversity of fluorinated building blocks and enable the synthesis of fluorinated drug analogs.

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