Enantioselective oxidative boron Heck reactions

Lee, Ai‐Lan

doi:10.1039/c5ob01984b

Cited by 72 publications

(37 citation statements)

References 76 publications

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“…We have been showcasing its applicability in the total synthesis of many biologically relevant molecules . Similar studies have been performed with oxidative Heck reactions, with boronic acids or boronates . Despite its maturity, the Heck reaction and its variations continue to demonstrate potential for further developments and applications in organic synthesis, mainly because the diastereo‐ and enantioselective versions of these reactions have now been progressing at unprecedented rates…”

Section: Introductionmentioning

confidence: 99%

“…[3] Similars tudies have been performed with oxidative Heck reactions, with boronic acids or boronates. [4] Despite its maturity,t he Heck reactiona nd its variations continuet od emonstrate potential for furtherd evelopmentsa nd applications in organic synthesis, mainly because the diastereo-and enantioselective versions of these reactions have now been progressing at unprecedented rates. [5] Since the seminal work of Hallberg and others, substrate-directable Heck reactions have constituted as pecialc hapter in this area.…”

Section: Introductionmentioning

confidence: 99%

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Enantioselective, Noncovalent, Substrate‐Directable Heck–Matsuda and Oxidative Heck Arylations of Unactivated Five‐Membered Carbocyclic Olefins

Oliveira

Angnes

Khan

et al. 2018

Chemistry A European J

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Highly diastereo- and enantioselective, noncovalent, substrate-directable Heck desymmetrizations of cyclopentenyl olefins containing hydroxymethyl and carboxylate functional groups are presented. These conformationally unbiased cyclic olefins underwent effective arylations in yields of up to 97 %, diastereoselectivity up to >20:1, and enantiomeric excesses of up to 99 %. Noncovalent directing effects were shown to be prevalent in both Heck-Matsuda and oxidative Heck reactions, allowing the preferential formation of cis-substituted aryl cyclopentenes containing two stereocenters, including quaternary stereocenters. These results further validate the internal out-of-coordination-sphere ion-dipole interaction concept directing the reaction diastereoselectivity to the cis-Heck product. This approach is complementary to existing methods using bis-phosphine monoxide ligands to give the opposite trans-diastereoisomer. The applicability of the method is showcased by the straightforward synthesis of a potent phosphodiesterase 4 inhibitor in a diastereo- and enantioselective manner. The reaction is operationally simple and has broad scope with regard to the nature of the arenediazonium salt and boronic acid employed. The mechanism and origin of stereoselectivity were investigated with control experiments and DFT calculations that fully supported the stabilizing internal out-of-coordination-sphere ion-dipole interaction between the resident functional group and cationic palladium.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Enantioselective, Noncovalent, Substrate‐Directable Heck–Matsuda and Oxidative Heck Arylations of Unactivated Five‐Membered Carbocyclic Olefins

Oliveira

Angnes

Khan

et al. 2018

Chemistry A European J

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“…Arylboronic acids are an important class of compounds for coupling reactions, which are stable in air and to moisture, and they are compatible with a broad range of common functional groups [62][63][64]. In 2015, Lu and co-workers presented the first oxidative Heck-type reactions of arylboronic acids with fluoroalkylated olefin [79].…”

Section: Scheme 17 Preparation Of Diazonium-functionalized Oligo(phementioning

confidence: 99%

“…Furthermore, the oxidative Heck cross-coupling reactions have become attractive for modern organic synthesis due to advantages such as efficiency, mild reaction conditions, good functional group tolerance, and widespread applications [62][63][64]. In 2017, Arvidsson and co-workers reported an operationally simple method for ligand-and additive-free oxidative Heck couplings of aryl boronic acids (57) with ESF (51) (Scheme 10) [65].…”

Section: Fluorine-containing Vinyl Sulfur Compounds As the Cross-coupmentioning

confidence: 99%

“…A plausible reaction mechanism was suggested in Scheme 21 [78]. The reaction presumably proceeded via (1) oxidative addition of aryldiazonium salt (106) to Pd(0), leading to an arylpalladium complex (110), (2) Arylboronic acids are an important class of compounds for coupling reactions, which are stable in air and to moisture, and they are compatible with a broad range of common functional groups [62][63][64]. In 2015, Lu and co-workers presented the first oxidative Heck-type reactions of arylboronic acids with fluoroalkylated olefin [79].…”

Section: Scheme 17 Preparation Of Diazonium-functionalized Oligo(phementioning

confidence: 99%

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Pd-Catalyzed Mizoroki-Heck Reactions Using Fluorine-Containing Agents as the Cross-Coupling Partners

Yang

Zhao

et al. 2018

Catalysts

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Abstract:The Mizoroki-Heck reaction represents one of the most convenient methods for carbon-carbon double bond formation in the synthesis of small organic molecules, natural products, pharmaceuticals, agrochemicals, and functional materials. Fluorine-containing organic compounds have found wide applications in the research areas of materials and life sciences over the past several decades. The incorporation of fluorine-containing segments into the target molecules by the Mizoroki-Heck reactions is highly attractive, as these reactions efficiently construct carbon-carbon double bonds bearing fluorinated functional groups by simple procedures. This review summarizes the palladium-catalyzed Mizoroki-Heck reactions using various fluorine-containing reagents as the cross-coupling partners. The first part of the review describes the Pd-catalyzed Mizoroki-Heck reactions of aryl halides or pseudo-halides with the fluorinated alkenes, and the second part discusses the Pd-catalyzed Mizoroki-Heck reactions of the fluorinated halides or pseudo-halides with alkenes. Variants of the Pd-catalyzed Mizoroki-Heck reactions with fluorine-containing reagents are also briefly depicted. This work supplies an overview, as well as a guide, to both younger and more established researchers in order to attract more attention and contributions in the realm of Mizoroki-Heck reactions with fluorine-containing participants.

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Oxidation and Reduction

Banerji¹

2020

Organic Reaction Mechanisms · 2016

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Enantioselective oxidative boron Heck reactions

Cited by 72 publications

References 76 publications

Enantioselective, Noncovalent, Substrate‐Directable Heck–Matsuda and Oxidative Heck Arylations of Unactivated Five‐Membered Carbocyclic Olefins

Enantioselective, Noncovalent, Substrate‐Directable Heck–Matsuda and Oxidative Heck Arylations of Unactivated Five‐Membered Carbocyclic Olefins

Pd-Catalyzed Mizoroki-Heck Reactions Using Fluorine-Containing Agents as the Cross-Coupling Partners

Oxidation and Reduction

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