60632-93-1

Upstream product

• 542-91-6 H₂SiEt₂ 
• 98-86-2 acetophenone 
• 98-85-1 1-Phenylethanol 

Downstream Products

• 864286-95-3 1-[2-(3-pyridyl)phenyl]ethanol 
• 87804-23-7 2-(1-hydroxyethyl)phenol 
• 94001-66-8 1-(2-benzyloxyphenyl)-1-ethanol 

Relevant academic research and scientific papers

Silylation reactions on nanoporous gold: Via homolytic Si-H activation of silanes

Si-H bond activation is an important process implicated in many useful synthetic applications including silylation and transfer hydrogenation reactions. Herein we discovered homolytic activation of Si-H bonds on the surface of nanoporous gold (NPG), forming hydrogen radicals and [Au]-[Si] intermediates. By virtue of this new reactivity, we achieved highly selective mono and sequential alcoholysis of dihydrosilane. In addition, the amphiphilic nature of the [Au]-[Si] intermediate allows for a new bis-silylation reaction of cyclic ethers. The present work showcased that the surface reactivity of nanocatalysts may provide exciting opportunity for new reaction discovery.

STABILIZATION OF ACTIVE METAL CATALYSTS AT METAL-ORGANIC FRAMEWORK NODES FOR HIGHLY EFFICIENT ORGANIC TRANSFORMATIONS

Metal-organic framework (MOFs) compositions based on post?synthetic metalation of secondary building unit (SBU) terminal or bridging OH or OH2 groups with metal precursors or other post-synthetic manipulations are described. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations, including the regioselective boryiation and siiylation of benzyiic C—H bonds, the hydrogenation of aikenes, imines, carbonyls, nitroarenes, and heterocycles, hydroboration, hydrophosphination, and cyclization reactions. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.

Bipyridine- and phenanthroline-based metal-organic frameworks for highly efficient and tandem catalytic organic transformations via directed C-H activation

We report here the synthesis of a series of robust and porous bipyridyl- and phenanthryl-based metal-organic frameworks (MOFs) of UiO topology (BPV-MOF, mBPV-MOF, and mPT-MOF) and their postsynthetic metalation to afford highly active single-site solid catalysts. While BPV-MOF was constructed from only bipyridyl-functionalized dicarboxylate linker, both mBPV- and mPT-MOF were built with a mixture of bipyridyl- or phenanthryl-functionalized and unfunctionalized dicarboxylate linkers. The postsynthetic metalation of these MOFs with [Ir(COD)(OMe)]2 provided Ir-functionalized MOFs (BPV-MOF-Ir, mBPV-MOF-Ir, and mPT-MOF-Ir), which are highly active catalysts for tandem hydrosilylation of aryl ketones and aldehydes followed by dehydrogenative ortho-silylation of benzylicsilyl ethers as well as C-H borylation of arenes using B2pin2. Both mBPV-MOF-Ir and mPT-MOF-Ir catalysts displayed superior activities compared to BPV-MOF-Ir due to the presence of larger open channels in the mixed-linker MOFs. Impressively, mBPV-MOF-Ir exhibited high TONs of up to 17000 for C-H borylation reactions and was recycled more than 15 times. The mPT-MOF-Ir system is also active in catalyzing tandem dehydrosilylation/dehydrogenative cyclization of N-methylbenzyl amines to azasilolanes in the absence of a hydrogen acceptor. Importantly, MOF-Ir catalysts are significantly more active (up to 95 times) and stable than their homogeneous counterparts for all three reactions, strongly supporting the beneficial effects of active site isolation within MOFs. This work illustrates the ability to increase MOF open channel sizes by using the mixed linker approach and shows the enormous potential of developing highly active and robust single-site solid catalysts based on MOFs containing nitrogen-donor ligands for important organic transformations.

Modular approach to reductive Csp2-H and Csp3-H silylation of carboxylic acid derivatives through single-pot, sequential transition metal catalysis

We report a modular approach to catalytic reductive Csp2-H and Csp3-H silylation of carboxylic acid derivatives encompassing esters, ketones, and aldehydes. Choice of either an Ir(I)/Rh(I) or Rh(I)/Rh(I) sequence leads to either exhaustive reductive ester or reductive ketone/aldehyde silylation, respectively. Notably, a catalyst-controlled direct formation of doubly reduced silyl ethers is presented, specifically via Ir-catalyzed exhaustive hydrosilylation. The resulting silyl ethers undergo Csp2-H and benzylic Csp3-H silylation in a single vessel.

Controlled hydrosilylation of carbonyls and imines catalyzed by a cationic aluminum alkyl complex

The synthesis, characterization, and unprecedented catalytic activity of cationic aluminum alkyl complexes toward hydrosilylation are described. X-ray crystallographic analysis of Tp*AlMe2 (1) and [Tp*AlMe][I3] (3) revealed the prefe

Iridium-catalyzed arene ortho -silylation by formal hydroxyl-directed C-H activation

A strategy for the ortho-silylation of aryl ketone, benzaldehyde, and benzyl alcohol derivatives has been developed in which a hydroxyl group formally serves as the directing element for Ir-catalyzed arene C-H bond activation. One-pot generation of a (hyd

Analysis of the enantioselectivities and initial rates of the hydrosilylation of acetophenone catalyzed by [Rh(cod)Cl]2/(chiral diphosphine). The quantitative analysis of ligand effects

Through the application of the quantitative analysis of ligand effects (QALE) method to the study of the hydrosilylation of acetophenone, we have shown, for the first time, that the initial rate and enantioselectivity of a complicated catalytic system responds in a rational manner to the variations in the stereoelectronic properties of the silane. The reactions (in benzene-d6 at 63 °C) were catalyzed by [Rh(cod)Cl]2/(chiral diphosphine) (chiral diphosphine=(R)-BINAP [(R)-(+)-2,2′-bis(diphenylphosphino)- 1,1′binaphthyl], (R,R)-tolyl-BINAP [(R)-(+)-2,2′-bis (di-p-tolylphosphino)-1,1′-binaphthyl], (R,R)-Me-DUPHOS [(R,R )-(-)-1,2-Bis-2,5-dimethylphospholano)benzene], (R,R)-DIOP [(R,R)-(-)-2,3-O-isopropylidine-2,3-dihydroxy-1,4-bis(diphenylphosphino) butane], and (R)-QUINAP [(R)-(+)-1-(2-diphenylphosphino-1-naphthyl) isoquinoline]. The ee's (R) of the hydrosilylation products (CH3CH(OSiR3)Ph) range between - 9 and 53% with the (R)-QUINAP giving the poorest enantioselectivity. The QALE analyses of log( R/S) for (R)-BINAP, (R)-tolyl-BINAP, (R,R)-Me-DUPHOS, and (R,R)-DIOP reveal that the steric effects associated with the silanes are not monotonic.