Enantioselective 1,1-Arylborylation of Alkenes: Merging Chiral Anion Phase Transfer with Pd Catalysis

Nelson, Hosea M.; Williams, Brett; Miró, Javier; Toste, F. Dean

doi:10.1021/jacs.5b00344

Cited by 151 publications

(72 citation statements)

References 40 publications

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“…264 The Pd-catalyzed three-component coupling of α-olefins, aryldiazonium salts, and bis(pinacolato)diboron provides the direct preparation of chiral …”

Section: Diazonium Saltsmentioning

confidence: 99%

Transition-Metal-Catalyzed Cleavage of C–N Single Bonds

et al. 2015

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“…264 The Pd-catalyzed three-component coupling of α-olefins, aryldiazonium salts, and bis(pinacolato)diboron provides the direct preparation of chiral …”

Section: Diazonium Saltsmentioning

confidence: 99%

Transition-Metal-Catalyzed Cleavage of C–N Single Bonds

et al. 2015

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“…Inspired by Toste and coworkers and their approach to an enantioselective 1,1-arylborylation reaction of alkenes, 6 we envisioned that coupling chiral anion phase transfer (CAPT) catalysis 7 with palladium catalysis could be applied to our system. In this process, an insoluble aryldiazonium salt 1 undergoes salt metathesis with a chiral phosphate anion (PA, 2 ) to form a soluble chiral ion pair (Scheme 1B).…”

Section: Introductionmentioning

confidence: 99%

“…Finally, transmetallation ( TM ) with B 2 pin 2 (in the Toste example) or arylboronic acid 3 , followed by reductive elimination ( RE ), restores the catalyst and releases the desired product (Scheme 1B). 4,6 …”

Section: Introductionmentioning

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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“…This phenomenon always plays a significant role in Phase transfer catalysis (PTC), especially in organic synthesis. Phase-transfer catalysis (PTC) is well known as a precious methodology in organic synthesis in modern years [3,4] . Phase-transfer catalysis (PTC) is a performance that was conducting a reaction between reactant species existing in homogeneous or heterogeneous method [5] .…”

Section: Introductionmentioning

confidence: 99%