Facile Synthesis of -Phosphinates from P(OR) or ClP(OR) via SiO-Promoted Hydrolysis.

-Phosphinates represent a valuable class of organophosphorus building blocks and catalytic ligands. The existing synthetic approaches are generally associated with the use of strong acids, the need for meticulous treatment of intermediates, and the limitation of only P-aryl introductions. Following a comprehensive investigation into the unexpected SiO-promoted hydrolysis observed during the chromatography workup of the crude R'P(OR) intermediates, we have developed an extremely simple and general synthetic route to -phosphinates from commercially available Grignard reagents and P(OR).

Stereoselective synthesis of ()-α,β-unsaturated esters: triethylamine-catalyzed allylic rearrangement of enol phosphates.

α,β-Unsaturated esters are key structural motifs widely distributed in various biologically active molecules, and their /-stereoselective synthesis has always been considered highly attractive in organic synthesis. Herein, we present a >99% ()-stereoselective one-pot synthetic approach towards β-phosphoroxylated α,β-unsaturated esters a mild trimethylamine-catalyzed 1,3-hydrogen migration of the corresponding unconjugated intermediates derived from the solvent-free Perkow reaction between low-cost 4-chloroacetoacetates and phosphites. Versatile β,β-disubstituted ()-α,β-unsaturated esters were thus afforded with full ()-stereoretentivity by cleavage of the phosphoenol linkage Negishi cross-coupling.

Synthesis of enol phosphates directly from ketones a modified one-pot Perkow reaction.

A modified Perkow reaction, named Perkow-Shi reaction, was developed based on the one-pot α-tosyloxylation of ketones following by addition of P(iii)-reagents and 4 Å molecular sieves. Diversity of enol phosphates, as well as enol phosphonates, enol phosphinates, and enol phosphoramidates were synthesized in high yields directly from the ubiquitously available ketones instead of the unfavourable α-chloroketones under a mild and environmental friendly condition.

Enantioselective Rhodium-Catalyzed Hydrogenation of ()--Sulfonyl-α-dehydroamido Boronic Esters.

Highly enantioselective rhodium-catalyzed hydrogenation of ()--sulfonyl-α-dehydroamido boronic esters is realized for the first time using a JosiPhos-type ligand. This method has enabled convenient synthesis of a series of enantio-enriched -sulfonyl-α-amido boronic esters in good yields and excellent enantioselectivities (up to 99% ee).

Fabrication of a β-cyclodextrin-based self-assembly containing a redox-responsive ferrocene.

The current research involves fabrication of a redox-responsive self-assembly system based on a ferrocene (Fc)-containing β-cyclodextrin (β-CD) derivative (βCD-EG-Fc). βCD-EG-Fc was synthesized, and its redox-sensitive self-assembly behavior was investigated using various techniques. On the basis of the intermolecular host-guest recognition between the β-CD group and the Fc moiety, βCD-EG-Fc primarily formed network-like structures and then vesicles following aging for a specified time.

Redox-responsive self-assembly of β-cyclodextrin and ferrocene double-headed amphiphilic molecules.

We present a redox-responsive self-assembly based on a unimolecular platform. Three double-headed amphiphilic molecules composed of β-cyclodextrin (β-CD) and ferrocene (Fc) each with an alkyl chain as a linker (βCD-C-Fc, m = 2, 6, and 10) were synthesized, and their self-assembly behaviors were investigated. The molecules self-assembled into polydisperse micelles that transformed into vesicles upon oxidization of the Fc moieties to Fc.