Expansion of the Concept of Nonlinear Effects in Catalytic Reactions Beyond Asymmetric Catalysis

Pollice, Robert; Schnürch, Michael

doi:10.1002/chem.201504970

Cited by 7 publications

(12 citation statements)

References 56 publications

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“…However, an unexpected NLE on the P:H ratio outcome was observed (Figure 1C). 11 As the enantiomeric ratio of 2b decreases, the P:H ratio erodes. This NLE could be explained with two reasonable possible scenarios (Figure 1D):…”

Section: Resultsmentioning

confidence: 99%

Mechanistic Investigations of the Pd(0)-Catalyzed Enantioselective 1,1-Diarylation of Benzyl Acrylates

et al. 2017

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A mechanistic study of the Pd-catalyzed enantioselective 1,1-diarylation of benzyl acrylates that is facilitated by a Chiral Anion Phase Transfer (CAPT) process is presented. Kinetic analysis, labeling, competition and non-linear effect experiments confirm the hypothesized general mechanism and reveal the role of the phosphate counterion in the CAPT catalysis. The phosphate was found to be involved in the phase transfer step and in the stereoinduction process as expected, but also in the unproductive reaction that provides the traditional Heck byproduct. Multivariate correlations revealed the CAPT catalyst’s structural features, affecting the production of this undesired byproduct, as well as weak interactions responsible for enantioselectivity. Such putative interactions include π-stacking and a CH···O electrostatic attraction between the substrate benzyl moiety and the phosphate. Analysis of the computed DFT transition structures for the stereodetermining step of the reaction supports the multivariate model obtained. The presented work provides the first comprehensive study of the combined use of CAPT and transition metal catalysis setting the foundation for future applications.

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Section: Resultsmentioning

confidence: 99%

Mechanistic Investigations of the Pd(0)-Catalyzed Enantioselective 1,1-Diarylation of Benzyl Acrylates

et al. 2017

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“…The first example from literature to be investigated is the Rh-catalyzed direct C-H amination of 2-phenylpyridines using organic azides (Scheme 3). 16 Scheme 3. Rh(III)-catalyzed direct C-H amination of 2-phenylpyridines with organic azides.…”

Section: Complexity A(t)-profile [A 0 -P(t)]-profile Catalyst Deactivmentioning

confidence: 99%

“…The authors performed detailed experimental and computational mechanistic studies and concluded that the TDTS is most likely one of the transition states leading to the postulated Rh(V) -nitrenoid intermediate, rather than the TS of C-H activation of 2-phenylpyridine. 16 Based on initial rate experiments, the kinetic model shown in Scheme 3b was proposed. 16 The TDI was suggested to be distributed between species 1 and 2, with complex 1 being predominant (Scheme 3).…”

Section: Complexity A(t)-profile [A 0 -P(t)]-profile Catalyst Deactivmentioning

confidence: 99%

“…16 Based on initial rate experiments, the kinetic model shown in Scheme 3b was proposed. 16 The TDI was suggested to be distributed between species 1 and 2, with complex 1 being predominant (Scheme 3). 16 The TDTS was proposed to be the step from 2 to 3, which is the product of amido insertion.…”

Section: Complexity A(t)-profile [A 0 -P(t)]-profile Catalyst Deactivmentioning

confidence: 99%

“…16 The TDI was suggested to be distributed between species 1 and 2, with complex 1 being predominant (Scheme 3). 16 The TDTS was proposed to be the step from 2 to 3, which is the product of amido insertion. Notably, computational studies showed this step to consist of several elementary reactions.…”

Section: Complexity A(t)-profile [A 0 -P(t)]-profile Catalyst Deactivmentioning

confidence: 99%

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A General Fitting Function to Estimate Apparent Reaction Orders of Kinetic Profiles

Pollice¹

2019

Preprint

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The rapid development of analytical methods in recent decades has resulted in a wide range of readily available and accurate reaction-monitoring techniques, which allow for easy determination of high-quality concentration-time data of chemical reactions. However, while the acquisition of kinetic data has become routine in the development of new chemical reactions and the study of their mechanisms, not all the information contained therein is utilized because of a lack of suitable analysis tools which unnecessarily complicates mechanistic studies. Herein, we report on a general method to analyze a single concentration-time profile of chemical reactions and extract information regarding the reaction order with respect to substrates, the presence of multiple kinetic regimes, and the presence of kinetic complexities, such as catalyst deactivation, product inhibition, and substrate decomposition.<br>

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Regioselective C3‐Phosphonation of Free Indoles via Transition‐Metal‐Free Radical/Hydrolysis Cascade

et al. 2019

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The selectivity is of great importance for the preparation of molecules in organic chemistry. Herein, a novel method to enable the highly regioselective C3‐phosphonation of free indoles has been developed. This transformation involves a radical and a hydrolysis procedure, and tolerates a range of functional groups, which gives an efficient route toward the 1H‐indol‐3 – ylphosphonic acid monoesters in one step.

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Expansion of the Concept of Nonlinear Effects in Catalytic Reactions Beyond Asymmetric Catalysis

Cited by 7 publications

References 56 publications

Mechanistic Investigations of the Pd(0)-Catalyzed Enantioselective 1,1-Diarylation of Benzyl Acrylates

Mechanistic Investigations of the Pd(0)-Catalyzed Enantioselective 1,1-Diarylation of Benzyl Acrylates

A General Fitting Function to Estimate Apparent Reaction Orders of Kinetic Profiles

Regioselective C3‐Phosphonation of Free Indoles via Transition‐Metal‐Free Radical/Hydrolysis Cascade

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