Mechanistic Studies on Nitrosation–Deaminocyclization of Mono-Carbamoylated Vicinal Amino Alcohols and Diols: A New Preparative In Situ Formation of Ethanediazo Hydroxide for the Ethylation of Carboxylates under Mild Conditions

2004 ◽  
Vol 77 (6) ◽  
pp. 1217-1227 ◽  
Author(s):  
Masumi Suzuki ◽  
Takeshi Sugai
Keyword(s):  
Amino Alcohols ◽  
Mechanistic Studies ◽  
Mild Conditions ◽  
In Situ Formation

scholarly journals Ultra-Small Pd(0) Nanoparticles into a Designed Semisynthetic Lipase: An Efficient and Recyclable Heterogeneous Biohybrid Catalyst for the Heck Reaction under Mild Conditions

Molecules ◽  
2018 ◽  
Vol 23 (9) ◽  
pp. 2358 ◽  
Author(s):  
David Lopez-Tejedor ◽  
Blanca de las Rivas ◽  
Jose M. Palomo
Keyword(s):  
Catalytic Activity ◽  
Protein Structure ◽  
Heck Reaction ◽  
Catalytic Performance ◽  
Reducing Agent ◽  
Chemically Modified ◽  
Mild Conditions ◽  
In Situ Formation ◽  
Geobacillus Thermocatenulatus

A novel heterogeneous enzyme-palladium (Pd) (0) nanoparticles (PdNPs) bionanohybrid has been synthesized by an efficient, green, and straightforward methodology. A designed Geobacillus thermocatenulatus lipase (GTL) variant genetically and then chemically modified by the introduction of a tailor-made cysteine-containing complementary peptide- was used as the stabilizing and reducing agent for the in situ formation of ultra-small PdNPs nanoparticles embedded on the protein structure. This bionanohybrid was an excellent catalyst in the synthesis of trans-ethyl cinnamate by Heck reaction at 65 °C. It showed the best catalytic performance in dimethylformamide (DMF) containing 10–25% of water as a solvent but was also able to catalyze the reaction in pure DMF or with a higher amount of water as co-solvent. The recyclability and stability were excellent, maintaining more than 90% of catalytic activity after five cycles of use.

scholarly journals Gold(I)-catalyzed intramolecular cyclization/intermolecular cycloaddition cascade as a fast track to polycarbocycles and mechanistic insights

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Cheng Zhang ◽  
Kemiao Hong ◽  
Chao Pei ◽  
Su Zhou ◽  
Wenhao Hu ◽  
...  
Keyword(s):  
Fast Track ◽  
Cycloaddition Reaction ◽  
Structural Diversity ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
In Situ Formation ◽  
Increasing Demand ◽  
High Yields ◽  
Synthetic Intermediate

AbstractMetal carbene is an active synthetic intermediate, which has shown versatile applications in synthetic chemistry. Although a variety of catalytic methods have been disclosed for the generation of carbene species from different precursors, there is an increasing demand for the development of efficient and practical approaches for the in-situ formation of metal carbene intermediates with structural diversity and unrevealed reactivity. Herein we report a gold-catalyzed cascade protocol for the assembly of polycarbocyclic frameworks in high yields under mild reaction conditions. Mechanistic studies indicate that the unique β-aryl gold-carbene species, generated via gold-promoted 6-endo-dig diazo-yne cyclization, is the key intermediate in this reaction, followed by a [4 + 2]-cycloaddition with external alkenes. In comparison to the well-documented metal carbene cycloadditions, this carbene intermediate serves as a 4-C synthon in a cycloaddition reaction. A variety of elusive π-conjugated polycyclic hydrocarbons (CPHs) with multiple substituents are readily accessible from the initially generated products by a mild oxidation procedure.

A Transient Directing Group Strategy Enables Enantioselective Reductive Heck Hydroarylation of Alkenes

2019 ◽  
Author(s):  
Lucas Oxtoby ◽  
Zi-Qi Li ◽  
Van Tran ◽  
Tuğçe Erbay ◽  
Ruohan Deng ◽  
...  
Keyword(s):  
Amino Acid ◽  
Transition Metal ◽  
Chiral Center ◽  
Computational Studies ◽  
Group Approach ◽  
Mild Conditions ◽  
Migratory Insertion ◽  
Directing Group ◽  
In Situ Formation

<p>Metal-coordinating directing groups have seen extensive use in the field of transition-metal-mediated functionalization of alkenes; however, their waste-generating installation and removal steps limit the efficiency and practicality of reactions that rely on their use. Inspired by developments in the field of C–H activation, herein we report a transient directing group approach to reductive Heck hydroarylation of alkenyl benzaldehyde substrates that proceeds under mild conditions. Highly stereoselective migratory insertion is facilitated by in situ formation of an imine from catalytic amounts of commercially available amino acid additive. Computational studies reveal an unusual mode of enantioinduction by the remote chiral center in the transient directing group.</p>

A Transient Directing Group Strategy Enables Enantioselective Reductive Heck Hydroarylation of Alkenes

2019 ◽  
Author(s):  
Lucas Oxtoby ◽  
Zi-Qi Li ◽  
Van Tran ◽  
Tuğçe Erbay ◽  
Ruohan Deng ◽  
...  
Keyword(s):  
Amino Acid ◽  
Transition Metal ◽  
Chiral Center ◽  
Computational Studies ◽  
Group Approach ◽  
Mild Conditions ◽  
Migratory Insertion ◽  
Directing Group ◽  
In Situ Formation

<p>Metal-coordinating directing groups have seen extensive use in the field of transition-metal-mediated functionalization of alkenes; however, their waste-generating installation and removal steps limit the efficiency and practicality of reactions that rely on their use. Inspired by developments in the field of C–H activation, herein we report a transient directing group approach to reductive Heck hydroarylation of alkenyl benzaldehyde substrates that proceeds under mild conditions. Highly stereoselective migratory insertion is facilitated by in situ formation of an imine from catalytic amounts of commercially available amino acid additive. Computational studies reveal an unusual mode of enantioinduction by the remote chiral center in the transient directing group.</p>

scholarly journals Formation of compact systems of super-Earths via dynamical instabilities and giant impacts

2019 ◽  
Vol 491 (4) ◽  
pp. 5595-5620 ◽  
Author(s):  
Sanson T S Poon ◽  
Richard P Nelson ◽  
Seth A Jacobson ◽  
Alessandro Morbidelli
Keyword(s):  
Initial Conditions ◽  
Post Processing ◽  
Significant Modification ◽  
Kepler Mission ◽  
Giant Impacts ◽  
Low Mass ◽  
In Situ Formation ◽  
Dynamical Instabilities ◽  
Gaseous Envelopes

ABSTRACT The NASA’s Kepler mission discovered ∼700 planets in multiplanet systems containing three or more transiting bodies, many of which are super-Earths and mini-Neptunes in compact configurations. Using N-body simulations, we examine the in situ, final stage assembly of multiplanet systems via the collisional accretion of protoplanets. Our initial conditions are constructed using a subset of the Kepler five-planet systems as templates. Two different prescriptions for treating planetary collisions are adopted. The simulations address numerous questions: Do the results depend on the accretion prescription?; do the resulting systems resemble the Kepler systems, and do they reproduce the observed distribution of planetary multiplicities when synthetically observed?; do collisions lead to significant modification of protoplanet compositions, or to stripping of gaseous envelopes?; do the eccentricity distributions agree with those inferred for the Kepler planets? We find that the accretion prescription is unimportant in determining the outcomes. The final planetary systems look broadly similar to the Kepler templates adopted, but the observed distributions of planetary multiplicities or eccentricities are not reproduced, because scattering does not excite the systems sufficiently. In addition, we find that ∼1 per cent of our final systems contain a co-orbital planet pair in horseshoe or tadpole orbits. Post-processing the collision outcomes suggests that they would not significantly change the ice fractions of initially ice-rich protoplanets, but significant stripping of gaseous envelopes appears likely. Hence, it may be difficult to reconcile the observation that many low-mass Kepler planets have H/He envelopes with an in situ formation scenario that involves giant impacts after dispersal of the gas disc.

scholarly journals Method for determining the thermal conductivity of in situ formation rock using drilling cuttings

AIP Advances ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 065015
Author(s):  
Fu Yi ◽  
Xupeng Qi ◽  
Xuexin Zheng ◽  
Huize Yu ◽  
Wenming Bai ◽  
...  
Keyword(s):  
Thermal Conductivity ◽  
In Situ Formation
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