Regioselective Copper-Catalyzed Boracarboxylation of Vinyl Arenes

Butcher, Trevor W.; McClain, Edward J.; Hamilton, Tyler G.; Perrone, Trina; Kroner, Kayla M.; Donohoe, Gregory C.; Akhmedov, Novruz G.; Petersen, Jeffrey L.; Popp, Brian V.

doi:10.1021/acs.orglett.6b03326

Cited by 96 publications

(70 citation statements)

References 58 publications

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“…In our original work, we noted significantly decreased boracarboxylation yields and high conversion of styrene upon reduced ICyCuCl catalyst loading (ICy=1,3‐bis(cyclohexyl)imadzol‐2‐ylidene) . We observed the same behavior with p ‐tBu‐styrene ( 1 a ), leading to boracarboxylation product ( 2 a) as well as trace amounts of hydro/protoboration ( 3 a ) and dehydrogenative borylation ( 4 a ) products; this substrate was chosen for screening purposes below (entry 1–2, Table ).…”

Section: Resultssupporting

confidence: 75%

“…Since CuCl/PPh 3 was catalytically active, albeit poorly, we thought that a more electron‐rich phosphine, such as PCy 3 paired with ICyCuCl, would produce a more competent secondary boracarboxylation catalyst upon primary catalyst decomposition . To our surprise, addition of PCy 3 led to slightly diminished catalytic reactivity (entry 6, Table ).…”

Section: Resultsmentioning

confidence: 99%

“…Having demonstrated that catalytic efficiency could be improved with addition of PPh 3 for an electron‐rich vinyl arene, we wanted to reassess the reactivity of strongly electron‐deficient vinyl arenes that were unreactive in our original work . Using p ‐CF 3 ‐styrene ( 1 b ) as the limiting reagent, we observed only trace amounts of boracarboxylation products with our originally published conditions .…”

Section: Resultsmentioning

confidence: 99%

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Beneficial Effect of a Secondary Ligand on the Catalytic Difunctionalization of Vinyl Arenes with Boron and CO₂

et al. 2019

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The boracarboxylation of vinyl arenes catalyzed by copper(I) is an alkene difunctionalization reaction that provides synthetically useful β‐boryl‐α‐aryl propanoic acid derivatives. Drawbacks of the original reaction methodology are high catalyst loading and vinyl arene scope limited largely to electron‐rich systems. Herein, we demonstrate that catalytic additives, specifically triphenylphosphine or electron‐rich styrene, leads to improved catalyst efficiency and broadening of substrate scope. With the addition of PPh3, comparable yields of previously reported boracarboxylated substrates as well as two novel β‐boronated non‐steroidal anti‐inflammatory drugs (bora‐fenoprofen and bora‐flurbiprofen) were achieved at lower catalyst loading. Boracarboxylation of electron‐deficient substrates could be achieved through superstoichiometric addition of vinyl arene or addition of secondary phosphine ligand. Reactivity optimization and competition experiments have provided preliminary insights into the ability of PPh3 to aid in the catalytic cycle, specifically carboxylation of electron‐rich benzyl‐copper(I) intermediate. Additional competition studies revealed that a catalytic amount of an electron‐rich vinyl arene could be used in addition to the copper(I) catalyst to promote boracarboxylation of an electron‐deficient styrene derivative.

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Section: Resultssupporting

confidence: 75%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Beneficial Effect of a Secondary Ligand on the Catalytic Difunctionalization of Vinyl Arenes with Boron and CO₂

et al. 2019

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“…Copper: In 2016, Popp and co-workers reported a regioselective copper-catalyzed boracarboxylation of styrenes with CO 2 and B 2 pin 2 [49]. The details of the reaction and the effect of the ligands were investigated by Lv et al in 2017 [50] (Fig.…”

Section: Addition At C Sp2mentioning

confidence: 99%

Carbon-carbon bonds with CO2: Insights from computational studies

Obst

Pavlovic

Hopmann

2018

Journal of Organometallic Chemistry

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a b s t r a c tIn this mini-review, we provide an overview of recent computational studies on homogeneous transition metal-catalyzed carbon-carbon bond formation with CO 2 . We cover substitution and addition reactions involving different metals (mainly Ni, Rh, Cu) and substrates (alkanes, alkenes, alkynes, arenes) with focus on the mechanistic details. The CO 2 insertion step is generally found to be rate-limiting. The reported transition state geometries for C-C bond formation mostly display three-membered cyclic arrangements involving the metal and the two reacting carbon atoms, except for reaction with C sp atoms, where acyclic conformations are observed. Other reported exceptions point to that an interaction of CO 2 with the metal catalyst may not be essential. Several studies suggest that Lewis acid additives could help activating CO 2 during C-C bond formation.

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“…Recently, Popp et al. described a copper‐catalyzed regioselective borylcarboxylation of styrenes with B 2 (pin) 2 and gaseous CO 2 . Under the reaction conditions, various β‐boryl α‐aryl propionic acids were obtained in moderate‐to‐excellent yields.…”

Section: Copper Catalysismentioning

confidence: 99%

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

Zhang

Liu

Chen

et al. 2018

Chemistry An Asian Journal

244

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Three-component reactions can directly convert three reactants into the desired products in one pot and thus greatly shorten the synthetic path. Recently, transition-metal catalysis has been applied in the difunctionalization of alkenes and remarkable progress has been achieved to facilitate the construction of a wide range of functional molecules with high atom- and step-economic efficiency. This Focus Review highlights recent advances in this field.

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Regioselective Copper-Catalyzed Boracarboxylation of Vinyl Arenes

Cited by 96 publications

References 58 publications

Beneficial Effect of a Secondary Ligand on the Catalytic Difunctionalization of Vinyl Arenes with Boron and CO₂

Beneficial Effect of a Secondary Ligand on the Catalytic Difunctionalization of Vinyl Arenes with Boron and CO₂

Carbon-carbon bonds with CO2: Insights from computational studies

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

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Regioselective Copper-Catalyzed Boracarboxylation of Vinyl Arenes

Cited by 96 publications

References 58 publications

Beneficial Effect of a Secondary Ligand on the Catalytic Difunctionalization of Vinyl Arenes with Boron and CO2

Beneficial Effect of a Secondary Ligand on the Catalytic Difunctionalization of Vinyl Arenes with Boron and CO2

Carbon-carbon bonds with CO2: Insights from computational studies

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

Contact Info

Product

Resources

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Beneficial Effect of a Secondary Ligand on the Catalytic Difunctionalization of Vinyl Arenes with Boron and CO₂

Beneficial Effect of a Secondary Ligand on the Catalytic Difunctionalization of Vinyl Arenes with Boron and CO₂