Highly diastereo- and enantioselective organocatalytic synthesis of trifluoromethylated erythritols based on the in situ generation of unstable trifluoroacetaldehyde.

Thus far, only a few methods for the asymmetric synthesis of erythritols bearing a trifluoromethyl group have been developed, and these methods present serious disadvantages such as the requirement of multiple steps for the preparation of their starting materials, low stereoselectivity, and the use of highly toxic reagents. Herein, we have developed a highly diastereo- and enantioselective organocatalytic method to synthesise erythritols bearing a trifluoromethyl group using (1) a commercially available organocatalyst to produce unstable trifluoroacetaldehyde in situ from its corresponding hemiacetal, followed by the simultaneous asymmetric carbon-carbon bond-forming reaction of the organocatalyst with an in situ-generated chiral enamine derived from 2,2-dimethyl-1,3-dioxane-5-one to obtain the corresponding aldol product in good yield (65-80%) with high diastereoselectivity (up to 94% de) and excellent enantioselectivity (up to >98% ee), (2) the highly diastereoselective reduction of the ketone moiety in the aldol product (up to 98% de), and (3) the deprotection of the acetal moiety.

A Rapid and Dual Optical CO2 -responsive Polydimethylsiloxane Elastomer with a Fluorinated Cyanine Dye.

We found that our optically CO2 -responsive polydimethylsiloxane (PDMS) elastomer rapidly and reversibly underwent both visible and fluorescent color changes in the presence of CO2 gas. Unlike conventional optically CO2 -responsive polymeric materials, it functions in totally dry gaseous conditions. The visible color and fluorescence of the elastomer sheet change after only 1 min of exposure to CO2 , and the sheet exhibits excellent repeatability in terms of color switching that persists for at least 20 times.

Aromatic fluorine atom-induced highly amine-sensitive trimethine cyanine dye showing colorimetric and ratiometric fluorescence change.

Herein, introducing multiple fluorine atoms into aromatic rings of trimethine cyanine dyes is proposed as a powerful method for dramatically increasing sensitivity to amines. The highly sensitive ratiometric fluorescence properties previously available only by intramolecular addition can be exploited in reactions with intermolecular amines or other nucleophiles.