165801-15-0

Upstream product

• 887616-75-3 (S)-(E)-4,4,4-trifluoro-1,3-diphenyl-2-butenyl acetate 
• 74-95-3 1,1-dibromomethane 
• 92533-92-1 (bromomethyl)lithium 
• 13652-07-8 phenyltrifluorodiazoethane 
• 78659-23-1 3,3,3-trifluoro-2-phenylpropionaldehyde 
• 103422-95-3 (S)-4-iso-propyl-3-(2'-phenylacetyl)oxazolidin-2-one 
• 434-45-7 2,2,2-Trifluoroacetophenone 
• 887616-73-1 (S)-(E)-4,4,4-trifluoro-1,3-diphenyl-2-buten-1-ol 
• 146801-38-9 (E)-4,4,4-trifluoro-1,3-diphenyl-2-buten-1-one 

Relevant academic research and scientific papers

HEME PROTEIN CATALYSTS FOR CARBON-BORON BOND FORMATION IN VITRO AND IN VIVO

Provided herein are methods for producing an organoboron product. The methods include combining a boron-containing reagent and a carbene precursor in the presence of a heme protein, e.g., a cytochrome c, a cytochrome P450, a globin, a protoglobin, a nitric oxide dioxygenase, a peroxidase, or a catalase, or a variant thereof, under conditions sufficient to form the organoboron product. Reaction mixtures for producing organoboron products are also described, as well as whole-cell catalysts comprising heme proteins and variants thereof for forming carbon-boron bonds.

Genetically programmed chiral organoborane synthesis

Recent advances in enzyme engineering and design have expanded nature's catalytic repertoire to functions that are new to biology1-3. However, only a subset of these engineered enzymes can function in living systems4-7. Finding enzymatic pathways that form chemical bonds that are not found in biology is particularly difficult in the cellular environment, as this depends on the discovery not only of new enzyme activities, but also of reagents that are both sufficiently reactive for the desired transformation and stable in vivo. Here we report the discovery, evolution and generalization of a fully genetically encoded platform for producing chiral organoboranes in bacteria. Escherichia coli cells harbouring wild-type cytochrome c from Rhodothermus marinus8 (Rma cyt c) were found to form carbon-boron bonds in the presence of borane-Lewis base complexes, through carbene insertion into boron-hydrogen bonds. Directed evolution of Rma cyt c in the bacterial catalyst provided access to 16 novel chiral organoboranes. The catalyst is suitable for gram-scale biosynthesis, providing up to 15,300 turnovers, a turnover frequency of 6,100 h-1, a 99:1 enantiomeric ratio and 100% chemoselectivity. The enantiopreference of the biocatalyst could also be tuned to provide either enantiomer of the organoborane products. Evolved in the context of whole-cell catalysts, the proteins were more active in the whole-cell system than in purified forms. This study establishes a DNA-encoded and readily engineered bacterial platform for borylation; engineering can be accomplished at a pace that rivals the development of chemical synthetic methods, with the ability to achieve turnovers that are two orders of magnitude (over 400-fold) greater than those of known chiral catalysts for the same class of transformation9-11. This tunable method for manipulating boron in cells could expand the scope of boron chemistry in living systems.

Homologative trifluoromethylation of acetals

Trifluoroethyl α-insertion of acetals has been developed. Aromatic, heteroaromatic, and alkenyl acetals react with in situ generated (trifluoromethyl)diazomethane in the presence of antimony(V) chloride to furnish α-trifluoromethyl acetals. A stereoselective version of this transformation exploiting the acetal as a chiral auxiliary is also presented. Georg Thieme Verlag Stuttgart · New York.

Palladium-catalyzed regio- and stereoselective formate reduction of fluorine-containing allylic mesylates. A new entry for the construction of a tertiary carbon attached with a fluoroalkyl group

The regioselective palladium-catalyzed formate reduction of γ-fluoroalkylated allylic esters is described. Reduction of the allylic esters under the influence of palladium with a monodentate phosphine ligand proceeded preferentially at the γ position, the corresponding reduction products with a fluoroalkyl group at the tertiary carbon being afforded in high yields. When the chiral allylic ester was employed, complete chirality transfer was observed, leading to the optically active materials in high yields.

Diastereoselective trifluoromethylation of chiral imide enolates with iodotrifluoromethane mediated by triethylborane

The trifluoromethylation of lithium enolates of chiral N-acyloxazolidinones with iodotrifluoromethane mediated by triethylborane proceeds with good diastereomeric excess.