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Stereospecific, Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling of Allylic Pivalates To Deliver Quaternary Stereocenters.

ABSTRACT: Recognizing the importance of all-carbon, quaternary stereocenters in complex molecule synthesis, a stereospecific, nickel-catalyzed cross-coupling of allylic pivalates with arylboroxines to deliver products equipped with quaternary stereocenters and internal alkenes was developed. The enantioenriched allylic pivalate starting materials are readily prepared, and a variety of functional groups can be incorporated on both the allylic pivalate and the arylboroxine. Additional advantages include the use of a commercially available and air-stable Ni(II) salt and BISBI ligand, mild reaction conditions, and high yields and ee's. The observed stereoinversion of this reaction is consistent with an open transition state in the oxidative addition step.

SUBMITTER: Cobb KM

PROVIDER: S-EPMC5576553 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature

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Stereospecific, Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling of Allylic Pivalates To Deliver Quaternary Stereocenters.

Cobb Kelsey M KM Rabb-Lynch Javon M JM Hoerrner Megan E ME Manders Alex A Zhou Qi Q Watson Mary P MP

Organic letters 20170807 16

Recognizing the importance of all-carbon, quaternary stereocenters in complex molecule synthesis, a stereospecific, nickel-catalyzed cross-coupling of allylic pivalates with arylboroxines to deliver products equipped with quaternary stereocenters and internal alkenes was developed. The enantioenriched allylic pivalate starting materials are readily prepared, and a variety of functional groups can be incorporated on both the allylic pivalate and the arylboroxine. Additional advantages include the ...[more]

PMID: 28783357

Similar Datasets

Accessing Both Retention and Inversion Pathways in Stereospecific, Nickel-Catalyzed Miyaura Borylations of Allylic Pivalates.

Project description:We have developed a stereospecific, nickel-catalyzed Miyaura borylation of allylic pivalates, which delivers highly enantioenriched α-stereogenic γ-aryl allylboronates with good yields and regioselectivities. Our complementary sets of conditions enable access to either enantiomer of allylboronate product from a single enantiomer of readily prepared allylic pivalate substrate. Excellent functional group tolerance, yields, regioselectivities, and stereochemical fidelities are observed. The stereochemical switch from stereoretention to stereoinversion largely depends upon solvent and can be explained by competitive pathways for the oxidative addition step. Our mechanistic investigations support a stereoretentive pathway stemming from a directed oxidative addition and a stereoinvertive pathway that is dominant when MeCN blocks coordination of the directing group by binding the nickel catalyst.

| S-EPMC5023504 | biostudies-literature

Nickel-Catalyzed Suzuki-Miyaura Coupling of Aliphatic Amides.

Project description:We report the Ni-catalyzed Suzuki-Miyaura coupling of aliphatic amide derivatives. Prior studies have shown that aliphatic amide derivatives can undergo Ni-catalyzed carbon-heteroatom bond formation but that Ni-mediated C-C bond formation using aliphatic amide derivatives has remained difficult. The coupling disclosed herein is tolerant of considerable variation with respect to both the amide-based substrate and the boronate coupling partner and proceeds in the presence of heterocycles and epimerizable stereocenters. Moreover, a gram-scale Suzuki-Miyaura coupling/Fischer indolization sequence demonstrates the ease with which unique polyheterocyclic scaffolds can be constructed, particularly by taking advantage of the enolizable ketone functionality present in the cross-coupled product. The methodology provides an efficient means to form C-C bonds from aliphatic amide derivatives using nonprecious-metal catalysis and offers a general platform for the heteroarylation of aliphatic acyl electrophiles.

| S-EPMC5906067 | biostudies-literature

Base-free nickel-catalysed decarbonylative Suzuki-Miyaura coupling of acid fluorides.

Project description:The Suzuki-Miyaura cross-coupling of organoboron nucleophiles with aryl halide electrophiles is one of the most widely used carbon-carbon bond-forming reactions in organic and medicinal chemistry1,2. A key challenge associated with these transformations is that they generally require the addition of an exogenous base, the role of which is to enable transmetallation between the organoboron nucleophile and the metal catalyst3. This requirement limits the substrate scope of the reaction because the added base promotes competitive decomposition of many organoboron substrates3-5. As such, considerable research has focused on strategies for mitigating base-mediated side reactions6-12. Previous efforts have primarily focused either on designing strategically masked organoboron reagents (to slow base-mediated decomposition)6-8 or on developing highly active palladium precatalysts (to accelerate cross-coupling relative to base-mediated decomposition pathways)10-12. An attractive alternative approach involves identifying combinations of catalyst and electrophile that enable Suzuki-Miyaura-type reactions to proceed without an exogenous base12-14. Here we use this approach to develop a nickel-catalysed coupling of aryl boronic acids with acid fluorides15-17, which are formed in situ from readily available carboxylic acids18-22. This combination of catalyst and electrophile enables a mechanistic manifold in which a 'transmetallation-active' aryl nickel fluoride intermediate is generated directly in the catalytic cycle13,16. As such, this transformation does not require an exogenous base and is applicable to a wide range of base-sensitive boronic acids and biologically active carboxylic acids.

| S-EPMC6212315 | biostudies-literature

Asymmetric Suzuki-Miyaura coupling of heterocycles via Rhodium-catalysed allylic arylation of racemates.

Project description:Using asymmetric catalysis to simultaneously form carbon-carbon bonds and generate single isomer products is strategically important. Suzuki-Miyaura cross-coupling is widely used in the academic and industrial sectors to synthesize drugs, agrochemicals and biologically active and advanced materials. However, widely applicable enantioselective Suzuki-Miyaura variations to provide 3D molecules remain elusive. Here we report a rhodium-catalysed asymmetric Suzuki-Miyaura reaction with important partners including aryls, vinyls, heteroaromatics and heterocycles. The method can be used to couple two heterocyclic species so the highly enantioenriched products have a wide array of cores. We show that pyridine boronic acids are unsuitable, but they can be halogen-modified at the 2-position to undergo reaction, and this halogen can then be removed or used to facilitate further reactions. The method is used to synthesize isoanabasine, preclamol, and niraparib-an anticancer agent in several clinical trials. We anticipate this method will be a useful tool in drug synthesis and discovery.

| S-EPMC5474734 | biostudies-literature

Reaction scope and mechanistic insights of nickel-catalyzed migratory Suzuki-Miyaura cross-coupling.

Project description:Cross-coupling reactions have developed into powerful approaches for carbon-carbon bond formation. In this work, a Ni-catalyzed migratory Suzuki-Miyaura cross-coupling featuring high benzylic or allylic selectivity has been developed. With this method, unactivated alkyl electrophiles and aryl or vinyl boronic acids can be efficiently transferred to diarylalkane or allylbenzene derivatives under mild conditions. Importantly, unactivated alkyl chlorides can also be successfully used as the coupling partners. To demonstrate the applicability of this method, we showcase that this strategy can serve as a platform for the synthesis of terminal, partially deuterium-labeled molecules from readily accessible starting materials. Experimental studies suggest that migratory cross-coupling products are generated from Ni(0/II) catalytic cycle. Theoretical calculations indicate that the chain-walking occurs at a neutral nickel complex rather than a cationic one. In addition, the original-site cross-coupling products can be obtained by alternating the ligand, wherein the formation of the products has been rationalized by a radical chain process.

| S-EPMC6972863 | biostudies-literature

Highly E-Selective, Stereoconvergent Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling of Alkenyl Ethers.

Project description:An improved method for the nickel-catalyzed Suzuki-Miyaura cross-coupling of alkenyl ethers is reported. This stereoconvergent protocol allows for the utilization of a wide range of alkenyl ethers and aryl boronic esters for the synthesis of variously substituted styrene derivatives. An olefinic mixture with respect to the alkenyl ethers can be employed, thereby circumventing the stereodefined synthesis of starting materials. Preliminary mechanistic investigations indicate a nickel-catalyzed olefin isomerization following initial stereoretentive cross-coupling.

| S-EPMC7025807 | biostudies-literature

Enantiospecific, nickel-catalyzed cross-couplings of allylic pivalates and arylboroxines.

Project description:We have developed an enantiospecific, nickel-catalyzed cross-coupling of unsymmetric 1,3-disubstituted allylic pivalates with arylboroxines. The success of this reaction relies on the use of BnPPh2 as a supporting ligand for the nickel(0) catalyst and NaOMe as a base. This method shows excellent functional group tolerance and broad scope in both the allylic pivalate and arylboroxine, enabling the preparation of 1,3-diaryl allylic products in high yields with excellent levels of regioselectivity and stereochemical fidelity.

| S-EPMC4084837 | biostudies-literature

Distal Ionic Substrate-Catalyst Interactions Enable Long-Range Stereocontrol: Access to Remote Quaternary Stereocenters through a Desymmetrizing Suzuki-Miyaura Reaction.

Project description:Spatial distancing of a substrate's reactive group and nonreactive catalyst-binding group from its pro-stereogenic element presents substantial hurdles in asymmetric catalysis. In this context, we report a desymmetrizing Suzuki-Miyaura reaction that establishes chirality at a remote quaternary carbon. The anionic, chiral catalyst exerts stereocontrol through electrostatic steering of substrates, even as the substrate's reactive group and charged catalyst-binding group become increasingly distanced. This study demonstrates that precise long-range stereocontrol is achievable by engaging ionic substrate-ligand interactions at a distal position.

| S-EPMC9549467 | biostudies-literature

Palladium-catalyzed chemoselective allylic substitution, Suzuki-Miyaura cross-coupling, and allene formation of bifunctional 2-B(pin)-substituted allylic acetate derivatives.

Project description:A formidable challenge at the forefront of organic synthesis is the control of chemoselectivity to enable the selective formation of diverse structural motifs from a readily available substrate class. Presented herein is a detailed study of chemoselectivity with palladium-based phosphane catalysts and readily available 2-B(pin)-substituted allylic acetates, benzoates, and carbonates. Depending on the choice of reagents, catalysts, and reaction conditions, 2-B(pin)-substituted allylic acetates and derivatives can be steered into one of three reaction manifolds: allylic substitution, Suzuki-Miyaura cross-coupling, or elimination to form allenes, all with excellent chemoselectivity. Studies on the chemoselectivity of Pd catalysts in their reactivity with boron-bearing allylic acetate derivatives led to the development of diverse and practical reactions with potential utility in synthetic organic chemistry.

| S-EPMC4219321 | biostudies-literature

Reductive Arylation of Amides via a Nickel-Catalyzed Suzuki-Miyaura-Coupling and Transfer-Hydrogenation Cascade.

Project description:We report a means to achieve the addition of two disparate nucleophiles to the amide carbonyl carbon in a single operational step. Our method takes advantage of non-precious-metal catalysis and allows for the facile conversion of amides to chiral alcohols via a one-pot Suzuki-Miyaura cross-coupling/transfer-hydrogenation process. This study is anticipated to promote the development of new transformations that allow for the conversion of carboxylic acid derivatives to functional groups bearing stereogenic centers via cascade processes.

| S-EPMC7855255 | biostudies-literature

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