Synthesis of β-Nitro Ketone from Geminal Bromonitroalkane and Silyl Enol Ether by Visible Light Photoredox Catalysis

Various β-nitro ketones, including those bearing a β-tertiary carbon, were prepared from geminal bromonitroalkanes and trimethylsilyl enol ethers of a broad range of ketones under visible light photoredox catalysis, which...

Homogeneous Gold Catalysis: Mechanistic Investigation of Hydroalkoxylation of Various Alkynes

<p>The reaction mechanism of the gold(III)-catalysed hydroalkoxylation of alkynes is studied to provide a deeper understanding of homogeneous gold catalysis. The study is conducted computationally using Density Functional Theory (DFT), with the PBE0 and BP86 functionals and basis sets of triple-ζ quality (aug-cc-pVTZ and aug-cc-pVTZ-PP for the gold atom). It emphasises the mechanisms undergone by various alkynes when they are activated by gold(III) catalysts towards nucleophilic attack to first form an enol ether and followed by a second nucleophilic attack to form a ketal as the final product. Hydrogen bonding networks formed by the solvent methanols are found to play a crucial role in the mechanism especially in the hydrogen migration steps that follow after the nucleophilic attacks. The first nucleophilic attacks are predicted to have rather low activation energies and hence they are expected to proceed fast while the second additions vary in activation barriers, depending on the steric effects in the substrates. The activation barrier for the last hydrogen migration is highest for all of the three reactions investigated and is expected to be the rate determining step. Investigations of internal alkyne reactions reveal that each elementary step requires a higher activation energy compared to terminal alkynes, which explains the low experimental rate of such reactions. Due to the regioselectivity problem in internal alkyne reactions, this results in a mixture of products which is difficult to isolate due to the similarities in their reaction energies. The study also highlights the calculated thermodynamics and kinetics of the reactions, which can be useful in predicting experimental outcomes. Arrhenius plots of concentration of each intermediate species against time were produced to further help the understanding of these mechanisms, whether or not the reactions go to full completion or stop at the formation of enol ether.</p>

Homogeneous Gold Catalysis: Mechanistic Investigation of Hydroalkoxylation of Various Alkynes

<p>The reaction mechanism of the gold(III)-catalysed hydroalkoxylation of alkynes is studied to provide a deeper understanding of homogeneous gold catalysis. The study is conducted computationally using Density Functional Theory (DFT), with the PBE0 and BP86 functionals and basis sets of triple-ζ quality (aug-cc-pVTZ and aug-cc-pVTZ-PP for the gold atom). It emphasises the mechanisms undergone by various alkynes when they are activated by gold(III) catalysts towards nucleophilic attack to first form an enol ether and followed by a second nucleophilic attack to form a ketal as the final product. Hydrogen bonding networks formed by the solvent methanols are found to play a crucial role in the mechanism especially in the hydrogen migration steps that follow after the nucleophilic attacks. The first nucleophilic attacks are predicted to have rather low activation energies and hence they are expected to proceed fast while the second additions vary in activation barriers, depending on the steric effects in the substrates. The activation barrier for the last hydrogen migration is highest for all of the three reactions investigated and is expected to be the rate determining step. Investigations of internal alkyne reactions reveal that each elementary step requires a higher activation energy compared to terminal alkynes, which explains the low experimental rate of such reactions. Due to the regioselectivity problem in internal alkyne reactions, this results in a mixture of products which is difficult to isolate due to the similarities in their reaction energies. The study also highlights the calculated thermodynamics and kinetics of the reactions, which can be useful in predicting experimental outcomes. Arrhenius plots of concentration of each intermediate species against time were produced to further help the understanding of these mechanisms, whether or not the reactions go to full completion or stop at the formation of enol ether.</p>

A Convenient Approach towards the Synthesis of ADMDP Type Iminosugars and Nojirimycin Derivatives from Sugar-Derived Lactams

An efficient method for the synthesis of nojirimycin- and pyrrolidine-based iminosugar derivatives has been developed. The strategy is based on the partial reduction in sugar-derived lactams by Schwartz’s reagent and tandem stereoselective nucleophilic addition of cyanide or a silyl enol ether dictated by Woerpel’s or diffusion control models, which affords amino-modified iminosugars, such as ADMDP or higher nojirimycin derivatives.

A Facile and Versatile Approach for the Synthesis of Degradable Polymers via Controlled Ring-Opening Metathesis Copolymerization

Norbornene derivatives (NBEs) are the most common monomers for ring-opening metathesis polymerization (ROMP) because they undergo living polymerization, yielding polymers with low dispersities and diverse functionalities. However, the all-carbon backbone of polyNBEs cannot be degraded. Polymer degradation is highly desired for many applications and has been a major limitation in ROMP chemistry. Here, we report a simple yet powerful method to synthesize controlled, degradable polymers by copolymerizing 2,3-dihydrofuran (DHF) with NBEs. DHF rapidly reacts with the Grubbs catalyst to form a thermodynamically stable Ru Fischer carbene, which is the only detectable active Ru species during the copolymerization, and the addition of NBEs becomes rate determining. This unique Ru Fischer carbene reactivity attenuates NBE homoaddition, which presented a significant challenge to previous copolymerization approaches, allows even incorporation of DHF units (acid-degradable enol ether bonds) throughout the copolymers, and thus enables complete polymer degradation while maintaining the favorable characteristics of living ROMP. We demonstrate the effective copolymerization of DHF with several types of NBEs to synthesize narrow-disperse polymers with tunable solubility, glass transition temperature, and mechanical properties. These polymers can all be fully degraded into small molecule or oligomeric species under mildly acidic conditions. This method can be readily adapted to traditional ROMP of widely used NBEs to synthesize new degradable polymers with tunable properties and facile degradation for various applications and environmental sustainability.