Dual-stimuli-responsive polymer-nanoreactors, P(S−M−NIP)/DC89PC@enzymes, were designed and constructed via enzymes encapsulation. The obviously improved enzymolysis efficiencies of the vesicle-based nanoreactors were real...
Boronyl Borinic Esters: Preparation as B2pin2/secBuLi/TFAA Adducts, Structural Insights and Reactivity in Pd‐catalyzed Allylic Borylation
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Novel class of diboron reagent – boronyl borinic ester – was developed that were generated as B2pin2/ sec BuLi/TFAA adducts. Detailed NMR with solid-state 2D NMR techniques and ESI-MS investigations were used to get structural insights of these new reagents. The new boronyl borinic esters were proved to be promising for allylic borylations of base-sensitive substrates.
Novel boronyl borinic ester I was generated by quenching the B2pin2/ sec BuLi-ate complex with trifluoroacetic acid anhydride (TFAA) via ring-opening in the 1,3,2-dioxaborolane moiety on ate-boron. Detailed NMR studies of the B2pin2/ sec BuLi-ate complex in solution and in solid state allowed us to assume its oligomeric nature in solids with only ate-boron involved in the oligomerization process. The O-trifluoroacetyl pinacolate residue on borinic ester I initially formed on quenching with TFAA undergoes an unusual intramolecular transesterification with the carbonyl group of trifluoroacetyl forming othroester moiety in a few hours at r. t. to give boronyl borinic ester II. A solution of these reagents I/II was proved to be efficient for borylation of (2-fluoroallyl)pyridinium salts that are highly base sensitive.Zum Volltext
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