77130-15-5

Upstream product

• 93-58-3 benzoic acid methyl ester 
• 13170-43-9 (trimethylsilyl)methylmagnesium chloride 
• 591-50-4 iodobenzene 
• 762-72-1 allyl-trimethyl-silane 
• 75-77-4 chloro-trimethyl-silane 
• 98-83-9 isopropenylbenzene 
• 13735-81-4 1-styrenyloxytrimethylsilane 
• 18243-38-4 (trimethylsilyl)methylmagnesium bromide 
• 98-86-2 acetophenone 
• 36963-72-1 (3-phenoxyprop-1-en-2-yl)benzene 
• 5769-02-8 2-methyl-2-phenyl[1,3]dithiolane 
• 108-86-1 bromobenzene 
• 135112-59-3 C₁₄H₃₅BOSi₃ 
• 917-64-6 methyl magnesium iodide 

Downstream Products

• 144053-84-9 (R)-1-Methyl-4-(2-phenyl-allyl)-4,5,6,7-tetrahydro-1H-benzo[c]isoxazol-3-one 
• 144053-84-9 (S)-1-Methyl-4-(2-phenyl-allyl)-4,5,6,7-tetrahydro-1H-benzo[c]isoxazol-3-one 
• 144053-85-0 (R)-1-Methyl-4-((E)-2-phenyl-propenyl)-4,5,6,7-tetrahydro-1H-benzo[c]isoxazol-3-one 
• 144053-85-0 (S)-1-Methyl-4-((E)-2-phenyl-propenyl)-4,5,6,7-tetrahydro-1H-benzo[c]isoxazol-3-one 
• 125315-70-0 (E)-1,5-Diphenyl-hexa-1,5-dien-3-ol 
• 14584-33-9 2,2,2-trifluoro-1-phenylethan-1-one 
• 1009632-27-2 C₂₁H₂₂O₂ 
• 10103-06-7 2,3-dimethoxynaphthalene 
• 1009632-16-9 C₂₀H₂₀ 
• 1009632-59-0 C₂₀H₂₀ 
• 91-57-6 2-Methylnaphthalene 
• 1009632-20-5 C₂₁H₂₂ 
• 581-40-8 2,3-dimethylnaphthalene 
• 1009632-63-6 C₂₀H₂₀O 

Relevant academic research and scientific papers

Enantioselective, Catalytic Multicomponent Synthesis of Homoallylic Amines Enabled by Hydrogen-Bonding and Dispersive Interactions

We report a one-step catalytic, enantioselective method for the preparation of homoallylic N-Boc amines directly from acetals. Reactive iminium ion intermediates are generated in situ through the combination of an acetal, a chiral thiourea catalyst, trialkylsilyl triflate, and N-Boc carbamate and are subsequently trapped by a variety of allylsilane nucleophiles. No homoallylic ether byproducts are detected, consistent with allylation of the iminium intermediate being highly favored over allylation of the intermediate oxocarbenium ion. Acetals derived from aromatic aldehydes possessing a variety of functional groups and substitution patterns yield homoallylic amines with excellent levels of enantiomeric enrichment. Experimental and computational data are consistent with an anchoring hydrogen-bond interaction between the protioiminium ion and the amide of the catalyst in the enantiodetermining transition state, and with stereodifferentiation achieved through specific noncovalent interactions (NCIs) with the catalyst pyrenyl moiety. Evidence is provided that the key NCI in the major pathway is a π-stacking interaction, contrasting with the cation-πinteractions invoked in previously studied reactions promoted by the same family of aryl-pyrrolidino-H-bond-donor catalysts.

An Electroreductive Approach to Radical Silylation via the Activation of Strong Si-Cl Bond

The construction of C(sp3)-Si bonds is important in synthetic, medicinal, and materials chemistry. In this context, reactions mediated by silyl radicals have become increasingly attractive but methods for accessing these intermediates remain limited. We present a new strategy for silyl radical generation via electroreduction of readily available chlorosilanes. At highly biased potentials, electrochemistry grants access to silyl radicals through energetically uphill reductive cleavage of strong Si-Cl bonds. This strategy proved to be general in various alkene silylation reactions including disilylation, hydrosilylation, and allylic silylation under simple and transition-metal-free conditions.

Enantioselective Synthesis of α-Allyl Amino Esters via Hydrogen-Bond-Donor Catalysis

We report a chiral-squaramide-catalyzed enantio- and diastereoselective synthesis of α-allyl amino esters. The optimized protocol provides access to N-carbamoyl-protected amino esters via nucleophilic allylation of readily accessible α-chloro glycinates. A variety of useful α-allyl amino esters were prepared, including crotylated products bearing vicinal stereocenters that are inaccessible through enolate alkylation, with high enantioselectivity (up to 97% ee) and diastereoselectivity (>10:1). The reactions display first-order kinetic dependence on both the α-chloro glycinate and the nucleophile, consistent with rate-limiting C-C bond formation. Computational analysis of the uncatalyzed reaction predicts an energetically inaccessible iminium intermediate, and a lower energy concerted SN2 mechanism.

Silver-promoted cross-coupling of substituted allyl(trimethyl)silanes with aryl iodides by palladium catalysis

A ligand-free Pd-catalyzed cross-coupling of substituted allyl(trimethyl)silanes with aryl iodides enabled by silver salts was developed. This reaction delivered allylic arenes chemoselectively and regioselectively. The study suggested that the reaction might proceed through oxidative addition of ArI to Pd(0) followed by halide abstraction to give an electrophilic complex ArPdX, which further reacted with allyl(trimethyl)silanes via electrophilic addition/desilylation/reductive elimination to afford the allyl-aryl coupling products.

A Stereoselective Reductive Hosomi-Sakurai Reaction

A novel reductive variant of the classical Hosomi-Sakurai reaction is reported. This transformation hinges on a redox-neutral, stereoselective internal reduction event under mild conditions. This operationally simple reaction relies on readily available starting materials and leads to useful products in diastereoselectivities of up to 7:1. The versatility of this new method is demonstrated through the stereoselective one-step synthesis of an AChE inhibitor.

Pd-Catalyzed C(sp3)-C(sp2) cross-coupling of Y(CH2SiMe3)3(THF)2 with vinyl bromides and triflates

Pd-Catalyzed C(sp3)-C(sp2) cross-coupling of Y(CH2SiMe3)3(THF)2 with vinyl bromides and triflates has been developed for efficient synthesis of various allyltrimethylsilanes. The cross-coupling reaction was conducted at room temperature with low catalyst loading of either Pd(PPh3)4 or Pd(PPh3)2Cl2, and exhibited high efficiency and a broad substrate scope. In combination with the cross-coupling by the Lewis-acid catalyzed Hosomi-Sakurai reaction, a novel three-component one-pot cascade reaction was then accomplished to deliver homoallylic alcohols and ethers with high regioselectivity and diastereoselectivity. The three-component reaction defined the yttrium complex as a novel one-carbon synthon, which could either trigger bifunctionalization of alkenes or link two electrophiles and would find applications in organic synthesis.

Palladium-catalyzed C(sp3)-C(sp2) cross-coupling of homoleptic rare-earth metal trialkyl complexes with aryl bromides: Efficient synthesis of functionalized benzyltrimethylsilanes

The first C(sp3)-C(sp2) cross-coupling of rare-earth metal alkyl complexes with aryl bromides has been developed. This reaction was conducted at low catalyst loading (0.5 mol%) and exhibited a broad substrate scope, thus providing a facile method for the synthesis of benzyltrimethylsilanes with diverse functional groups.

Nickel catalyzed dealkoxylative Csp2-Csp3 cross coupling reactions - Stereospecific synthesis of allylsilanes from enol ethers

The application of cyclic and acyclic enol ethers as electrophiles in cross coupling reactions offers new possibilities for the preparation of functional compounds. A novel nickel catalyzed dealkoxylative cross coupling reaction allows access to structurally diverse allylsilanes and alcohol derivatives with high stereospecificity and in good yields under mild reaction conditions directly from the corresponding enol ethers.

Copper-catalyzed trifluoromethylation of allylsilanes

CF3 on Csp3: Trifluoromethylation of allylsilane derivatives was accomplished through the use of CuI and Togni's reagent (1) under mild conditions. The reaction of allylsilanes without a substituent in the 2-position gave vinylsilane derivative

Asymmetric counteranion-directed catalytic hosomi-sakurai reaction

Counteranion control enables the enantioselective, organo Lewis acid catalyzed Hosomi-Sakurai reaction of (hetero)aromatic aldehydes and allylsilanes using an easily handled disulfonimide precatalyst (see scheme). The key to the success of this system is to turn the usually undesired silylium ion catalysis into the desired catalytic regime and pair the cation with an enantiopure disulfonimide anion, thereby applying the concept of asymmetric counteranion-directed catalysis.