82482-05-1

Upstream product

• 66107-29-7 4-methoxyphenyl triflate 
• 762-72-1 allyl-trimethyl-silane 
• 696-62-8 para-iodoanisole 
• 1450-14-2 1,1,1,2,2,2-hexamethyldisilane 
• 53484-50-7 (E)-p-methoxy-cinnamyl alcohol 
• 140-67-0 Estragole 
• 16029-98-4 trimethylsilyl iodide 
• 637-69-4 4-Methoxystyrene 
• 123-11-5 4-methoxy-benzaldehyde 

Downstream Products

• 78387-60-7 (3R*,4S*)-3,4-Bis(4-methoxyphenyl)-1-hexene 
• 88932-44-9 (3R*,4R*)-3,4-Bis(4-methoxyphenyl)-1-hexene 

Relevant academic research and scientific papers

A Bench-Stable, Single-Component Precatalyst for Silyl-Heck Reactions

Studies of the silyl-Heck reaction aimed at identifying active palladium complexes have revealed a new species that is formed in situ. This complex has been identified as the palladium iodide dimer, [(JessePhos)PdI2]2, which has been

Orthogonally protected 1,2-diols from electron-rich alkenes using metal-free olefin syn-dihydroxylation

A new method for the stereoselective metal-free syn-dihydroxylation of electron-rich olefins is reported, involving reaction with TEMPO/IBX in trifluoroethanol (TFE) or hexafluoroisopropanol (HFIP) and the addition of a suitable nucleophile. Orthogonally

Rational design of a second generation catalyst for preparation of allylsilanes using the silyl-Heck reaction

Using rational ligand design, we have developed of a second-generation ligand, bis(3,5-di-tert-butylphenyl)(tert-butyl)phosphine, for the preparation of allylsilanes using the palladium-catalyzed silyl-Heck reaction. This new ligand provides nearly complete suppression of starting material alkene isomerization that was observed with our first-generation catalyst, providing vastly improved yields of allylsilanes from simple alkene starting materials. The studies quantifying the electronic and steric properties of the new ligand are described. Finally, we report an X-ray crystal structure of a palladium complex resulting from the oxidative addition of Me3SiI using an analogous ligand that provides significant insight into the nature of the catalytic system.

Preparation of allyl and vinyl silanes by the palladium-catalyzed silylation of terminal olefins: A silyl-heck reaction

Installing silicon is easy! A high-yielding protocol for the palladium-catalyzed silylation of terminal alkenes is reported. This method allows facile conversion of styrenes to E-β-silyl styrenes by using iodotrimethylsilane (TMSI) or chlorotrimethylsilane/lithium iodide (see scheme). Terminal allyl silanes with good E/Z ratios are also readily accessed from α-olefins.

Palladium-catalyzed allylic C-OH functionalization for efficient synthesis of functionalized allylsilanes

A new method is described for palladium-catalyzed allylic silylation using allylic alcohols and disilanes as precursors. The reactions proceed smoothly under mild and neutral conditions, and this method is suitable for synthesis of regioand stereodefined allylsilanes. The presented silylation reaction can be easily extended to include synthesis of allylboronates by change of the dimetallic reagent. The presented synthetic procedure offers a broad platform for the selective synthesis of functionalized allyl metal reagents, which are useful precursors in advanced organic chemistry and natural product synthesis.

Asymmetric, anti-selective scandium-catalyzed Sakurai additions to glyoxyamide. Applications to the syntheses of N-Boc D-alloisoleucine and D-isoleucine

An enantio- and diastereoselective Sakurai-Hosomi reaction, catalyzed by chiral scandium pyridyl-bis(oxazoline) (pybox) complexes, has been developed. Both alkyl- and aryl-substituted allylsilanes are effective coupling partners with N-phenylglyoxamide. Applications of this reaction to the asymmetric syntheses of N-Boc D-alloisoleucine and D-isoleucine are described.

Tetraalkylammonium salt-based catalyst systems for directing Heck-type reactions. Arylation of allyltrimethylsilane

An appropriate selection of the [Pd/base/QX] catalyst systems allows one to direct at will the palladium-catalysed arylation of allyltrimethylsilane towards the formation of either (E)-1-aryl-3-(trimethylsilyl)-1-propene or 3-aryl-1-propene, by preventing

Highly Regioselective Palladium-Catalyzed Internal Arylation of Allyltrimethylsilane with Aryl Triflates

Highly regioselective ligand-controlled Heck-arylation reactions of allyltrimethylsilane, delivering branched β-products, were performed in moderate to good yields. The high preference for internal over terminal double-bond arylation suggests a contributi

Preparation of allylsilanes via cross-metathesis

Allylsilanes are prepared by simple metathetical cross-coupling of terminal olefins with allyltrimethylsilane. Allyltrimethylsilane coupling with π-substituted terminal olefins (styrenes, 1-phenyl-1,3-butadiene, and acrylonitrile) proceeds in excellent yi

Silicon-Mediated Synthesis of Bibenzyl Systems: Synthesis of Ring and Side-Chain Functionalized Hexestrol Derivatives

Derivatives of hexestrol , a non-steroidal estrogen, bearing photochemically reactive functional groups or γ-emmitting radionuclides, are useful as affinity labeling agents for the estrogen receptor or as imaging agents for receptor positive breast tumors, respectively.We have developed convenient synthetic routes to two side chain functionalized and aromatic ring functionalized hexestrol derivatives, based on a direct benzylic coupling reaction mediated by allylsilanes or silyl ketene acetals. 1-Dehydrohexestrol and variousaromatic ring substituted 1-dehydrohexestrol derivatives can be prepared by coupling 3-(trimethylsilyl)-1-(4-methoxyphenyl)propene with various reactive benzylic derivatives, and pentestrol derivatives are prepared by the coupling of the silyl ketene acetal derivative of p-methoxyphenyl acetic ester with benzylic derivatives.The R*,S* (erythro) and R*,R* (threo) diastereomers formed in each case can be separated readily by chromatography and recrystallization.This silicon-mediated approach to functionalized hexestrol derivatives provides a convenient route to many compounds of interest as biochemical probes and receptor-based diagnostic reagents.