Код: Выделить всё
Under nitrogen, the freshly prepared chlorophosphoric acid ester (1.56mmol)from
2,2-dihydroxy-3,3-dimethyl-1,1-biphenyl was dissolved in 6ml THF, cool to -30ዊ,
0.5ml triethylamine(3.12mmol) and 10mg DMAP in THF 1ml was added dropwise,
the reation was stirred for 30min, then the diol(2) 100mg(0.78mmol) in 3ml THF was
added dropwise at -30ዊ and the mixture was allowed to warm to room temperature
and stirred for 24h. filtrated and the filtration was passed through a short alumina
column(d=0.5cm, L=3cm), removed solution at reduced pressure, a white solid
390mg(90%) was get:Код: Выделить всё
A 10 ml Schelenk flask was charged with 100mg(0.78mmol) of diol 2 20mg DMAP,
160mg(1.6mmol)triethylamine and 5ml THF under nitrogen. The mixture was stirred
and the solution was cooled to 0 ዊ . A solution of 0.3ml
chlorodiphenylphosphine(1.56mmol) in 2ml THF was added drop-wise with stirring,
then stirred at RT for 24h.. Filtrated, and removed the solution in vacuo, the crude
product was purified through flash-chromatography give pure product as a thick
liguidКод: Выделить всё
In a glove box, to a solution of [Rh(COD)2]BF4 (5mg, 0.012mmol) in 10ml CH2Cl2 was
added chiral ligand (0.015mmol). After stirring the mixture for 20min, the
substrate(1.2mmol) was added. The hydrogenation was performed at room temperature
under 1atm of hydrogen for 12h. GC-MS to test the conversation, the reaction mixture
was concentrated in vacuo. The residue was eluted off a short silica gel
column(ethyl-acetate/n-hexane=1:1) to remove the catalyst, remove the solvent in
vacuo to get pure product as a white solid.
