Alkene epoxidation catalysed by camphor-derived β-ketophosphonate complexes of molybdenum(VI)

Can the Stereogenic 1,1’‐Bi‐2‐naphtol Molecule Be Coordinated to W(VI) or Mo(VI) Peroxo Moieties?

“…With the aim of tailoring asymmetric molecular catalysts for alkene epoxidation, several works have reported the use of H 2 binol or its derivatives with e. g . Mo(VI), [7–11] W(VI), [8,9,11] Mn(II), [12] Os(VI), [9] V(V), [8] Zr(IV) [8] and Ti(IV) [8,13] . As regards Mo(VI), Griffith et al .…”

“…[1][2][3][4][5] For example, enantiomers of 1,1'-bi-2naphtol, denoted H 2 binol, or substituted derivatives have been extensively studied as possible stereogenic ligands, [6] although for the peculiar case of enantioselective alkene epoxidation, most of the reported studies rely on bi-or tetra-dentate N,Ohetero-donor ligands. [5] With the aim of tailoring asymmetric molecular catalysts for alkene epoxidation, several works have reported the use of H 2 binol or its derivatives with e. g. Mo(VI), [7][8][9][10][11] W(VI), [8,9,11] Mn(II), [12] Os(VI), [9] V(V), [8] Zr(IV) [8] and Ti(IV). [8,13] As regards Mo(VI), Griffith et al have described the synthesis and the X-ray structure of the cis-dioxo [MoO 2 (binol)(acac)] À but no indication was given on the reactivity of this compound towards hydrogen peroxide and no catalysis result was presented.…”

In situ grafting of cyclopentadienyl-molybdenum complexes on mesoporous materials: The reaction of [η5-CpMo(CO)3]−Na+ with surface fixed iodo-benzyl siloxane

“…A variety of molybdenum (VI) complexes are known to be versatile catalysts for the oxidation of organic substrates [1][2][3][4][5][6][7][8][9]. Molybdenum based catalysts were applied for the industrial epoxidation of propylene, utilizing tbutyl hydroperoxide (TBHP) as oxidizing agent since the late 1960s [10,11].…”

Regiospecific Vinyl Phosphate/β-Keto Phosphonate Rearrangements Initiated by Halogen−Metal Exchange

“…This rearrangement has given access to phosphonates inaccessible or impossible to prepare by classical methods, including some derived from nonracemic ketones . The product phosphonates have proven useful as intermediates for synthesis of natural products and some analogues, as nonracemic ligands for transition metal catalysts and as substrates for further studies of the reactivity of β-keto phosphonates . At the same time, efforts to trap the intermediate anions have met with limited success and with unsymmetrical ketones a mixture of regioisomers may result from the rearrangement.…”