79294-34-1

Upstream product

• 69178-10-5 2-styryl-1,3-dithiane 
• 766-77-8 Dimethylphenylsilane 
• 873-49-4 cyclopropylbenzene 
• 768-33-2 phenyldimethylsilyl chloride 
• 16519-25-8 (E)-cinnamyl phenyl ether 
• 1145-98-8 1,2-diphenyltetramethyldisilane 
• 876657-72-6 (Z)-cinnamyl phenyl ether 
• 21087-29-6 trans-3-phenylprop-2-enyl chloride 
• 21040-45-9 Cinnamyl acetate 
• 50555-04-9 cinnamyl benzoate 
• 28315-20-0 (E)-cinnamic N-phenyl carbamate 
• 106625-69-8 ethyl (E)-3-phenyl-2-propenyl carbonate 
• 85669-63-2 (E)-cinnamyl diethyl phosphate 
• 4392-24-9 Cinnamyl bromide 

Downstream Products

• 140-29-4 phenylacetonitrile 

Relevant academic research and scientific papers

Manganese-Catalyzed Dehydrogenative Silylation of Alkenes following Two Parallel Inner-Sphere Pathways

We report on an additive-free Mn(I)-catalyzed dehydrogenative silylation of terminal alkenes. The most active precatalyst is the bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dippe)(CO)3(CH2CH2CH3)]. The catalytic process is initiated by migratory insertion of a CO ligand into the Mn-alkyl bond to yield an acyl intermediate which undergoes rapid Si-H bond cleavage of the silane HSiR3 forming the active 16e- Mn(I) silyl catalyst [Mn(dippe)(CO)2(SiR3)] together with liberated butanal. A broad variety of aromatic and aliphatic alkenes was efficiently and selectively converted into E-vinylsilanes and allylsilanes, respectively, at room temperature. Mechanistic insights are provided based on experimental data and DFT calculations revealing that two parallel reaction pathways are operative: an acceptorless reaction pathway involving dihydrogen release and a pathway requiring an alkene as sacrificial hydrogen acceptor.

Donor Rhodium Carbenes by Retro-Buchner Reaction

Rhodium carbenes are key intermediates in a range of cycloadditions and insertion reactions. Herein, we report the first generation of donor RhII carbenes by decarbenation of 7-substituted 1,3,5-cycloheptatrienes. This discovery unlocks an improved retro-Buchner-cyclopropanation sequence, a Si?H insertion reaction for a broad-scope synthesis of allylsilanes, and a new method for the vinylogation of aldehydes. The last strategy led to the development of an iterative synthesis of E-polyenes, and to the total synthesis of navenones B and C.

Silicon Grignard Reagents as Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution

A broad range of transition-metal catalysts is shown to promote allylic substitution reactions of allylic electrophiles with silicon Grignard reagents. The procedure was further elaborated for CuI as catalyst. The regioselectively is independent of the leaving group for primary allylic precursors, favoring α over γ. The stereochemical course of this allylic transposition was probed with a cyclic system, and anti -dia-stereoselectivity was obtained.

Synthesis and reactions of donor cyclopropanes: efficient routes to cis- and trans-tetrahydrofurans

Abstract A detailed study on the synthesis and reactions of silylmethylcyclopropanes is reported. In their simplest form, these donor-only cyclopropanes undergo Lewis acid promoted reaction to give either cis- or trans-tetrahydrofurans, with the selectivity being reaction condition-dependant. The adducts themselves are demonstrated to be an important scaffold for structural diversification. The combination of a silyl-donor group in a donor-acceptor cyclopropane with novel acceptor groups is also discussed.

Silylative cyclopropanation of allyl phosphates with silylboronates

A potassium-bis(trimethylsilyl)amide-mediated cyclopropanation of allyl phosphates with silylboronates has been developed. Unlike the reported copper-catalyzed allylic substitution reactions, the nucleophile selectively attacks at the β-position of the allylic substrates under the present reaction conditions. The mechanism of this process has also been investigated, thus indicating the involvement of a silylpotassium species as the active nucleophilic component.

Rhodium(II)-catalyzed stereoselective synthesis of allylsilanes

The rhodium-catalyzed decomposition of 2-(triisopropylsilyl)ethyl aryl- and vinyldiazoacetates results in the stereoselective formation of Z-allylsilanes. The transformation is considered to proceed by silyl-directed intramolecular C-H functionalization to form a β-lactone intermediate followed by a silyl-activated extrusion of carbon dioxide.

Enantioselective synthesis of α-tri- and α-tetrasubstituted allylsilanes by copper-catalyzed asymmetric allylic substitution of allyl phosphates with silylboronates

A copper/N-heterocyclic carbene-catalyzed asymmetric allylic substitution of allyl phosphates with a silylboronate has been developed to give highly enantioenriched allylsilanes. High regioselectivity has been achieved by employing NaOH as the base, and this catalyst system is effective for both γ-mono- and disubstituted allyl phosphates.

Asymmetric synthesis of α-chiral allylic silanes by enantioconvergent γ-selective copper(I)-catalyzed Allylic Silylation

Gamma way: Regio- and enantioselective allylic substitution with a silicon nucleophile generated by copper(I)-catalyzed Si-B bond activation provides direct access to α-chiral allylic silanes from linear acceptors. The enantioconvergent catalysis employing McQuade's six-membered N-heterocyclic-carbene-copper(I) catalyst is applicable to aryl- and alkyl-substituted allylic phosphates (see scheme). Copyright

Surfactant-Enabled Transition Metal-Catalyzed Chemistry

In one embodiment, the present application discloses mixtures comprising (a) water in an amount of at least 1% wt/wt of the mixture; (b) a transition metal catalyst; and (c) one or more solubilizing agents; and methods for using such mixtures for performing transition metal mediated bond formation reactions.

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.