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Dual Ni/photoredox-catalyzed asymmetric cross-coupling to access chiral benzylic boronic esters.

ABSTRACT: The flourishing Ni/photoredox-catalyzed asymmetric couplings typically rely on redox-neutral reactions. In this work, we report a reductive cross-coupling of aryl iodides and α-chloroboranes under a dual catalytic regime to further enrich the metallaphotoredox chemistry. This approach proceeds under mild conditions (visible light, ambient temperature, no strong base) to access the versatile benzylic boronic esters with good functional group tolerance and excellent enantioselectivities.

SUBMITTER: Zheng P

PROVIDER: S-EPMC7954797 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Facile access to functionalized chiral secondary benzylic boronic esters <i>via</i> catalytic asymmetric hydroboration.

Project description:Allylic and homoallylic phosphonates bearing an aryl or heteroaryl substituent at the γ- or δ-position undergo rhodium-catalyzed asymmetric hydroboration by pinacolborane to give functionalized chiral secondary benzylic boronic esters in yields up to 86% and enantiomer ratios up to 99 : 1. Compared to minimally-functionalized terminal and 1,1-disubstituted vinyl arenes, there are relatively few reports of efficient catalytic asymmetric hydroboration (CAHB) of more highly functionalized internal alkenes. Phosphonate substrates bearing a variety of common heterocyclic ring systems, including furan, indole, pyrrole and thiophene derivatives, as well as those bearing basic nitrogen substituents (e.g., morpholine and pyrazine) are tolerated, although donor substituents positioned in close proximity of the alkene can influence the course of the reaction. Stereoisomeric (E)- and (Z)-substrates afford the same major enantiomer of the borated product. Deuterium-labelling studies reveal that rapid (Z)- to (E)-alkene isomerization accounts for the observed (E/Z)-stereoconvergence during CAHB. The synthetic utility of the chiral boronic ester products is illustrated by stereospecific C-B bond transformations including stereoretentive electrophile promoted 1,2-B-to-C migrations, stereoinvertive SE2 reactions of boron-ate complexes with electrophiles, and stereoretentive palladium- and rhodium-catalyzed cross-coupling protocols.

| S-EPMC6520923 | biostudies-literature

Direct Synthesis of Secondary Benzylic Alcohols Enabled by Photoredox/Ni Dual-Catalyzed Cross-Coupling.

Project description:An operationally simple, mild, redox-neutral method for the cross-coupling of α-hydroxyalkyltrifluoroborates is reported. Utilizing an Ir photocatalyst, α-hydroxyalkyl radicals are generated from the single-electron oxidation of the trifluoroborates, and these radicals are subsequently engaged in a nickel-catalyzed C-C bond-forming reaction with aryl halides. The process is highly selective, functional group tolerant, and step economical, which allows the direct synthesis of secondary benzylic alcohol motifs.

| S-EPMC5732067 | biostudies-literature

Palladium Catalyzed Asymmetric Three-Component Coupling of Boronic Esters, Indoles, and Allylic Acetates.

Project description:Boronic esters react with 2-lithiated indoles to form boronate intermediates. The boronate reacts with allylic acetates in the presence of (BINAP)Pd catalysts to allylate C3 concurrent with alkyl migration from B to C2 of the indole. Overall, the process is a three-component coupling that joins an allylic acetate, and indole and an organo-B(pin) species to provide substituted indoles and indolines with high enantio-, regio-, and diastereoselectivity.

| S-EPMC5572568 | biostudies-literature

Phosphonate-Directed Catalytic Asymmetric Hydroboration: Delivery of Boron to the More Substituted Carbon, Leading to Chiral Tertiary Benzylic Boronic Esters.

Project description:Phosphonate-directed catalytic asymmetric hydroboration (CAHB) of β-aryl/heteroaryl methylidenes and trisubstituted alkenes by pinacolborane enables facile access to functionalized, chiral tertiary benzylic boronic esters. Hydroboration is catalyzed by a chiral rhodium catalyst prepared in situ from a Rh(I)-precursor in combination with a simple TADDOL-derived chiral cyclic monophosphite in a 1:1 ratio. The regio- and stereochemistry arises from the combined effects of the relative disposition of the directing group to the alkene, the alkene substitution pattern, and the necessity of an aryl substituent attached to the alkene. A range of aryl and heteroaryl substituents can be accommodated, and for several chiral substrates, the reactions are efficiently catalyst-controlled enabling the choice of diastereomeric products as desired. Stereospecific transformations of the chiral boronic ester afford chiral phosphonates bearing a quaternary carbon stereocenter. The synthetic utility of the products is further demonstrated by α-oxidation of the phosphonate leading to hydroxy- and oxo-phosphonates; the latter readily undergo elimination/substitution reactions to unmask the phosphonate functionality with the formation of aldehydes, alcohols, esters, amides, acids and ketones.

| S-EPMC6533611 | biostudies-literature

Photoredox Cross-Coupling: Ir/Ni Dual Catalysis for the Synthesis of Benzylic Ethers.

Project description:Single-electron transmetalation has emerged as an enabling paradigm for the cross-coupling of Csp(3) hybridized organotrifluoroborates. Cross-coupling of ?-alkoxymethyltrifluoroborates with aryl and heteroaryl bromides has been demonstrated by employing dual catalysis with a combination of an iridium photoredox catalyst and a Ni cross-coupling catalyst. The resulting method enables the alkoxymethylation of diverse (hetero)arenes under mild, room-temperature conditions.

| S-EPMC4854197 | biostudies-literature

Mechanism and Origins of Ligand-Controlled Stereoselectivity of Ni-Catalyzed Suzuki-Miyaura Coupling with Benzylic Esters: A Computational Study.

Project description:Nickel catalysts have shown unique ligand control of stereoselectivity in the Suzuki-Miyaura cross-coupling of boronates with benzylic pivalates and derivatives involving C(sp3)-O cleavage. The SIMes ligand (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) produces the stereochemically inverted C-C coupling product, while the tricyclohexylphosphine (PCy3) ligand delivers the retained stereochemistry. We have explored the mechanism and origins of the ligand-controlled stereoselectivity with density functional theory (DFT) calculations. The oxidative addition determines the stereoselectivity with two competing transition states, an SN2 back-side attack type transition state that inverts the benzylic stereogenic center and a concerted oxidative addition through a cyclic transition state, which provides stereoretention. The key difference between the two transition states is the substrate-nickel-ligand angle distortion; the ligand controls the selectivity by differentiating the ease of this angle distortion. For the PCy3 ligand, the nickel-ligand interaction involves mainly ?-donation, which does not require a significant energy penalty for the angle distortion. The facile angle distortion with PCy3 ligand allows the favorable cyclic oxidative addition transition state, leading to the stereoretention. For the SIMes ligand, the extra d-p back-donation from nickel to the coordinating carbene increases the rigidity of the nickel-ligand bond, and the corresponding angle distortion is more difficult. This makes the concerted cyclic oxidative addition unfavorable with SIMes ligand, and the back-side SN2-type oxidative addition delivers the stereoinversion.

| S-EPMC5607113 | biostudies-literature

Synthesis of Chiral Tertiary Boronic Esters by Oxime-Directed Catalytic Asymmetric Hydroboration.

Project description:Chiral boronic esters are useful intermediates in asymmetric synthesis. We have previously shown that carbonyl-directed catalytic asymmetric hydroboration (CAHB) is an efficient approach to the synthesis of functionalized primary and secondary chiral boronic esters. We now report that the oxime-directed CAHB of alkyl-substituted methylidene and trisubstituted alkene substrates by pinacolborane (pinBH) affords oxime-containing chiral tertiary boronic esters with yields up to 87% and enantiomeric ratios up to 96:4 e.r. The utility of the method is demonstrated by the formation of chiral diols and O-substituted hydroxylamines, the generation of quaternary carbon stereocenters through carbon-carbon coupling reactions, and the preparation of chiral 3,4,4-trisubstituted isoxazolines.

| S-EPMC4878850 | biostudies-literature

Ni-catalyzed asymmetric hydrogenation of N-aryl imino esters for the efficient synthesis of chiral α-aryl glycines.

Project description:Chiral α-aryl glycines play a key role in the preparation of some bioactive products, however, their catalytic asymmetric synthesis is far from being satisfactory. Herein, we report an efficient nickel-catalyzed asymmetric hydrogenation of N-aryl imino esters, affording chiral α-aryl glycines in high yields and enantioselectivities (up to 98% ee). The hydrogenation can be conducted on a gram scale with a substrate/catalyst ratio of up to 2000. The obtained chiral N-p-methoxyphenyl α-aryl glycine derivatives are not only directly useful chiral secondary amino acid esters but can also be easily deprotected by treatment with cerium ammonium nitrate for further transformations to several widely used molecules including drug intermediates and chiral ligands. Formation of a chiral Ni-H species in hydrogenation is detected by 1H NMR. Computational results indicate that the stereo selection is determined during the approach of the substrate to the catalyst.

| S-EPMC7683563 | biostudies-literature

Nickel-Catalyzed Cross-Coupling of Redox-Active Esters with Boronic Acids.

Project description:A transformation analogous in simplicity and functional group tolerance to the venerable Suzuki cross-coupling between alkyl-carboxylic acids and boronic acids is described. This Ni-catalyzed reaction relies upon the activation of alkyl carboxylic acids as their redox-active ester derivatives, specifically N-hydroxy-tetrachlorophthalimide (TCNHPI), and proceeds in a practical and scalable fashion. The inexpensive nature of the reaction components (NiCl2 ?6?H2 O-$9.5?mol(-1) , Et3 N) coupled to the virtually unlimited commercial catalog of available starting materials bodes well for its rapid adoption.

| S-EPMC5232357 | biostudies-literature

Synthesis of Chiral Tertiary Boronic Esters: Phosphonate-Directed Catalytic Asymmetric Hydroboration of Trisubstituted Alkenes.

Project description:Highly enantioselective rhodium-catalyzed hydroboration of allylic phosphonates by pinacolborane affords chiral tertiary boronic esters. The β-borylated phosphonates are readily converted to chiral β- and γ-hydroxyphosphonates and aminophosphonates and to phosphonates bearing a quaternary carbon stereocenter. The utility of the latter is illustrated by the synthesis of (S)-(+)-bakuchiol methyl ether.

| S-EPMC5423446 | biostudies-literature

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