15895-87-1

Upstream product

• 23556-91-4 1-((1-(benzyloxy)propoxy)methyl)benzene 
• 55775-43-4 2-Chloro-3,4-epoxy-4-phenylbutane 
• 14593-43-2 benzyl allyl ether 
• 100-51-6 benzyl alcohol 
• 71-36-3 butan-1-ol 
• 250234-79-8 (1-benzyloxy-allyl)-trimethyl-silane 
• 201230-82-2 carbon monoxide 
• 20194-18-7 sodium phenyl-methanolate 

Downstream Products

• 111160-14-6 1-(benzyloxy)-1-(prop-2-enyloxy)propane 
• 100-51-6 benzyl alcohol 
• 1021903-15-0 1-phenyl-1-benzyloxy-1-propene 
• 84736-38-9 (E)-1-(benzyloxy)-1-(prop-1-enyloxy)propane 
• 84736-39-0 (Z)-1-(benzyloxy)-1-(prop-1-enyloxy)propane 

Relevant academic research and scientific papers

A polymer-supported iridium catalyst for the stereoselective isomerisation of double bonds

A polymer-supported iridium catalyst has been prepared and used in the isomerisation of the double bonds in aryl allylic derivatives with excellent trans selectivity and without the need for conventional work-up procedures.

A Novel Probe for Free-radical Intermediates

C-C bond cleavage of oxiranes, which is triggered by adjacent homolysis but not heterolysis, occurs at a sufficiently rapid rate to be a useful probe for free-radical intermediates in chemical and biological systems.

Photo-triggered hydrogen atom transfer from an iridium hydride complex to unactivated olefins

Many photoactive metal complexes can act as electron donors or acceptors upon photoexcitation, but hydrogen atom transfer (HAT) reactivity is rare. We discovered that a typical representative of a widely used class of iridium hydride complexes acts as an H-atom donor to unactivated olefins upon irradiation at 470 nm in the presence of tertiary alkyl amines as sacrificial electron and proton sources. The catalytic hydrogenation of simple olefins served as a test ground to establish this new photo-reactivity of iridium hydrides. Substrates that are very difficult to activate by photoinduced electron transfer were readily hydrogenated, and structure-reactivity relationships established with 12 different olefins are in line with typical HAT reactivity, reflecting the relative stabilities of radical intermediates formed by HAT. Radical clock, H/D isotope labeling, and transient absorption experiments provide further mechanistic insight and corroborate the interpretation of the overall reactivity in terms of photo-triggered hydrogen atom transfer (photo-HAT). The catalytically active species is identified as an Ir(ii) hydride with an IrII-H bond dissociation free energy around 44 kcal mol-1, which is formed after reductive 3MLCT excited-state quenching of the corresponding Ir(iii) hydride, i.e. the actual HAT step occurs on the ground-state potential energy surface. The photo-HAT reactivity presented here represents a conceptually novel approach to photocatalysis with metal complexes, which is fundamentally different from the many prior studies relying on photoinduced electron transfer. This journal is

Highly regioselective hydroformylation with hemispherical chelators

The hemispherical diphosphites (R,R)- or (S,S)-5,11,17,23-tetratert-butyl- 25,27-di(OR)-26,28-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy) -calix[4]arene (R = OPr, OCH2Ph, OCH2-naphtyl, O-fluorenyl; R = H, R' = OPr) (LR), all with C2 symmetry, have been synthesised starting from the appropriate di-O-alkylated calix[4]-arene precursor. In the presence of [Rh(acac)(CO)2], these ligands straightforwardly provide chelate complexes in which the metal centre sits in a molecular pocket defined by two naphthyl planes related by the C 2 axis and the two apically situated R groups. Hydroformylation of octene with the LPr/Rh system turned out to be highly regioselective, the linear-to-branched (l:b) aldehyde ratio reaching 58:1. The l:b ratio significantly increased when the propyl groups were replaced by -CH 2Ph (l:b = 80) or -CH2naphthyl (1:b = 100) groups, that is, with substituents able to sterically interact with the apical metal sites, but without inducing an opening of the cleft nesting the catalytic centre. The trend to preferentially form the aldehyde the shape of which fits with the shape of the catalytic pocket was further confirmed in the hydroformylation of styrene, for which, in contrast to catalysis with conventional diphosphanes, the linear aldehyde was the major product (up to ca. 75 % linear aldehyde). In the hydroformylation of frarts-2-octene with the Lbenzyl/ Rh system, combined isomerisation/hydroformylation led to a remarkably high 1:b aldehyde ratios of 25, thus showing that isomerisation is more effective than hydroformylation. Unusually large amounts of linear products were also observed with all the above diphosphites in the tandem hydroformylation/amination of styrene (1:b of ca. 3:1) as well as in the hydroformylation of allyl benzyl ether (1:b ratio up to 20).

A selective and convenient ruthenium mediated method for the synthesis of mixed acetals and orthoesters

Addition of alcohols and phenols to O-allyl compounds (allyl ethers and acrolein acetals), catalyzed by [RuCl2(PPh3)3], was examined. Intramolecular addition of an OH group, leading to the formation of cyclic acetals and o

Studies on the synthesis of Richardianidin-1 via the tautomer-arrested annulation of Fischer carbene complexes

A strategy for the synthesis of richardianidin-1 is evaluated which has as its key step the tautomer-arrested annulation of chromium-carbene complexes. Both inter- and intramolecular variations of the strategy are examined. The intramolecular reaction involves the tethering of the alkyne to the oxygen stabilizing substituent of the carbene carbon. The outcome of the intramolecular tautomer-arrested annulation was found to be highly dependent on the nature of the tether and the on the type of substituent on the alkyne. The product distribution from these reactions included the desired hydrindenone resulting from tautomer-arrested annulation, a naphthalenedione, and a spirocyclohexadienone. The latter two products result from CO insertion prior to cyclization. The optimal tether length for the tautomer-arrested product is four atoms between the alkyne and the carbene carbon. The yields for the intramolecular reaction dropped significantly for a substituent on the alkyne terminus that was larger than a methyl group and this was not suitable for a synthesis of richardianidin-1. Initial studies on the intermolecular tautomer-arrested annulation focused on the regioselectivity of alkyne incorporation. The reaction with isopropyl(methyl)acetylene gives a single regioisomer and reveals that the tautomer-arrested annulation is more regioselective than the normal benzannulation. Furthermore, the intermolecular reaction is more tolerant of larger substituents on the terminus of the alkyne. As a result of the studies on the intermolecular tautomer-arrested annulation a suitable alkyne was found that introduces all of the carbons present in the six-membered lactone of richardianidin-1. Georg Thieme Verlag Stuttgart.

Synthesis and fluoride-promoted Wittig rearrangements of α-alkoxysilanes

(matrix presented) Lewis acid-catalyzed reaction of allyl and benzyl trichloroacetimidates with α-silyl alcohols was found to be a general method for the synthesis of α-alkoxysilanes. Upon exposure to CsF, these α-alkoxysilanes could be made to undergo [2,3]-Wittig rearrangement with an efficiency similar to that realized by the analogous but inherently more toxic α-alkoxystannanes.

Triisobutylaluminum-Assisted Reductive Rearrangement of Alkyl 1-Alkenyl Acetals: An Easy Synthesis of β-Alkoxy Alcohols

Alkyl 1-alkenyl acetals react with Al-i-Bu3 to give very good yields of β-alkoxy alcohols through a reductive rearrangement.The reaction is totally regioselective, but no stereocontrol occurs.