In situ and reactor study of the enantioselective hydrogenation of acetylacetone by ruthenium catalysis with the new chiral diphosphine ligand (R)-(R)-3-benzyl-2,4-bis(diphenylphosphino)pentane
C. Bianchini et al., In situ and reactor study of the enantioselective hydrogenation of acetylacetone by ruthenium catalysis with the new chiral diphosphine ligand (R)-(R)-3-benzyl-2,4-bis(diphenylphosphino)pentane, ORGANOMETAL, 19(13), 2000, pp. 2450-2461
The new optically pure C-1-symmetric diphosphine ligand (R)-(R)-3-benzyl-2,
4-bis(diphenylphosphino)pentane (BDPBzP) has been synthesized by enantiosel
ective reduction of 3-benzyl-2,4-pentanedione with [((S)-BINAP)Ru(p-cymene)
Cl]Cl, followed by the reaction of potassium diphenylphosphide with the bis
(mesylate) intermediate (S)-(S)-PhCH2CH(CH-(OMs)CH3)(2). The Ru(II) complex
es [(BDPBzP)Ru(p-cymene)I]I . 2CH(2)Cl(2) (5), [(BDPBzP)-(DMSO)Ru(mu-Cl)(3)
RuCl(BDPBzP)] (6a), and [(BDPBzP)Ru(Cl(CH3CN)(3)]OTf (7) have been prepared
and characterized by multinuclear NMR spectroscopy The p-cymene complex 5
has been authenticated by a single-crystal X-ray analysis. All Ru(II) compl
exes are effective catalyst precursors for the enantioselective hydrogenati
on of acetylacetone to (R)-(R)-2,4-pentanediol. The best catalytic performa
nce in terms of enantioselective discrimination tee's up to 99%) has been o
bserved for the dimer 6a, An in situ high-pressure NMR study in catalytic c
onditions has shown that the nonclassical polyhydride dimer [(BDPBzP)(eta(2
)-H-2)ClRu(mu-H)(2)RuCl(eta(2)-H-2)(BDPBzP)] is the only species observed a
ll over the catalytic cycle, The monohydrogenated intermediate (R)-4-hydrox
ypentan-2-one is obtained in appreciable yields only at low temperature or
low conversion. The relative yields and ee's of the mono-and dihydrogenated
products are consistent with the effect of a double stereodifferentiation
process.