The first examples of the enantioselective Heck–Matsuda reaction: arylation of unactivated cyclic olefins using chiral bisoxazolines

Correia, Carlos Roque Duarte; Oliveira, Caio C.; Salles, Airton G.; Santos, Elisabete

doi:10.1016/j.tetlet.2012.04.079

Cited by 79 publications

(40 citation statements)

References 34 publications

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“…[4] The reaction was completed in 30 min at 60 8C, and, contrary to our initial expectations, we obtained two products which were readily isolated and purified by flash chromatography in a combined yield of 63 %. [4] The reaction was completed in 30 min at 60 8C, and, contrary to our initial expectations, we obtained two products which were readily isolated and purified by flash chromatography in a combined yield of 63 %.…”

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confidence: 75%

“…[1,2] The enantioselective Heck reaction has been a pivotal tool in organic synthesis, with new versions bringing significant advances to the field. [4] Later on, this enantioselective arylation was applied to both butene-diol isomers 4 on route to the synthesis of valuable aryl-lactones 6, as shown in Scheme 1. [3] In 2012, we reported the first example of an enantioselective Heck-Matsuda reaction: the desymmetrization of unactivated olefin 2 employing the chiral bisoxazoline ligand L1.…”

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Stereoselective Synthesis of Aryl Cyclopentene Scaffolds by Heck–Matsuda Desymmetrization of 3‐Cyclopentenol

Angnes

Oliveira

et al. 2014

Chemistry A European J

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A new enantioselective Heck-Matsuda desymmetrization reaction was accomplished by using 3-cyclopentenol to produce chiral five-membered 4-aryl cyclopentenol scaffolds in good yields and high ee's, together with some 3-aryl-cyclopentanones as minor products. Mechanistically, the hydroxyl group of 3-cyclopentenol acts as a directing group and is responsible for the cis- arrangement in the formation of the 4-aryl-cyclopentenols.

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confidence: 99%

Stereoselective Synthesis of Aryl Cyclopentene Scaffolds by Heck–Matsuda Desymmetrization of 3‐Cyclopentenol

Angnes

Oliveira

et al. 2014

Chemistry A European J

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“…Functional groups such as esters and carboxylic acids were also evaluated and found to be less effective in directing the Heck arylation in the cyclopentene scaffold. A previous report from our group on the Heck–Matsuda arylation of ester 9 a indicated essentially no diastereoselectivity and only moderate enantioselectivity, although the reaction could be carried out in good yield . Curiously, a carboxylic ester was used by Zhou and Liu as a model compound for a conventional Heck arylation (triflate and bis‐phosphine monoxide ligand) and the trans ‐Heck product was obtained as the almost exclusive diastereomer .…”

Section: Resultsmentioning

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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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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“…Fort hese reasons,m ost applications in total synthesis were based on intramolecular variants where the substrate bias provides high level of regiocontrol (Scheme 1a). [4][5][6] Then ewly formed stereogenic centers in the carbopalladation step were preserved owing to the high preference of the palladium hydride species for migration along the carbon chain followed by conversion of the alcohol into an aldehyde group (Scheme 1c). [3] An ew development in this field was the arylation of acyclica lkenyl alcohols recently reported independently by Sigman and Correia using aryldiazonium salts as electrophiles.…”

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Quaternary Stereogenic Centers through Enantioselective Heck Arylation of Acyclic Olefins with Aryldiazonium Salts: Application in a Concise Synthesis of (R)‐Verapamil

2015

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We describe herein ah ighly regio-and enantioselective Pd-catalyzed Heck arylation of unactivated trisubstituted acyclic olefins to provide all-carbon quaternary stereogenic centers.C hiral N,Nligands of the pyrimidine-and pyrazino-oxazoline class were developed for that purpose, providing the desired products in good to high yields with enantiomeric ratios up to > 99:1. Both linear and branched substituents on the olefins were well-tolerated. The potential of this new method is demonstrated by the straightforward synthesis of several O-methyl lactols and lactones containing quaternary stereocenters,together with aconcise enantioselective total synthesis of the calcium channel blocker verapamil.

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The first examples of the enantioselective Heck–Matsuda reaction: arylation of unactivated cyclic olefins using chiral bisoxazolines

Cited by 79 publications

References 34 publications

Stereoselective Synthesis of Aryl Cyclopentene Scaffolds by Heck–Matsuda Desymmetrization of 3‐Cyclopentenol

Stereoselective Synthesis of Aryl Cyclopentene Scaffolds by Heck–Matsuda Desymmetrization of 3‐Cyclopentenol

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

Quaternary Stereogenic Centers through Enantioselective Heck Arylation of Acyclic Olefins with Aryldiazonium Salts: Application in a Concise Synthesis of (R)‐Verapamil

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