Asymmetric synthesis of allylic compoundsviahydrofunctionalisation and difunctionalisation of dienes, allenes, and alkynes

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(7), P. 2060 - 2118

Published: Jan. 1, 2020

This review article provides an overview of progress in asymmetric synthesis allylic compoundsviahydrofunctionalisation and difunctionalisation dienes, allenes, alkynes.

Language: Английский

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Stereodivergent Coupling of 1,3-Dienes with Aldimine Esters Enabled by Synergistic Pd and Cu Catalysis

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(37), P. 14554 - 14559

Published: Sept. 3, 2019

Herein we describe the use of synergistic Pd and Cu catalysis for stereodivergent coupling reactions between 1,3-dienes aldimine esters. By using different enantiomers two metal catalysts, all four stereoisomers products, which have vicinal stereocenters, could be accessed with high diastereo- enantioselectivity. This atom-economical cross-coupling reaction has a wide substrate scope good functional group tolerance. Our work highlights power asymmetric involving Pd-hydride catalysts.

Language: Английский

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Stereodivergent Allylation of Azaaryl Acetamides and Acetates by Synergistic Iridium and Copper Catalysis

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(4), P. 1239 - 1242

Published: Jan. 10, 2018

We report stereodivergent allylic substitution reactions of esters with prochiral enolates derived from azaaryl acetamides and acetates to form products addition the at most substituted carbon an allyl moiety two catalysts, a chiral metallacyclic iridium complex bisphosphine-ligated copper(I) complex, which individually control configuration electrophilic nucleophilic atoms, respectively. By simple permutations enantiomers all four stereoisomers containing stereogenic centers were synthesized high diastereoselectivity enantioselectivity. A variety bearing pyridyl, benzothiazolyl, benzoxazolyl, pyrazinyl, quinolinyl isoquinolinyl moieties found be suitable for this transformation.

Language: Английский

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Catalytic Enantio- and Regioselective Addition of Nucleophiles in the Intermolecular Hydrofunctionalization of 1,3-Dienes

ACS Catalysis, Journal Year: 2019, Volume and Issue: 10(2), P. 1060 - 1076

Published: Dec. 12, 2019

Catalytic enantioselective synthesis of small-molecule building blocks with allylic stereogenic centers is an important objective in organic synthesis, but preparing this motif wherein the adjacent olefin 1,2-disubstituted a single step tremendous challenge. Late-transition-metal-catalyzed intermolecular couplings nucleophiles and 1,3-dienes hydrofunctionalization reactions have quickly emerged as compelling approach to these related compounds. In Perspective, we illustrate how diene hydrofunctionalizations provided avenue complex, highly desirable chemical space that not readily accessed by other technologies. We also aim provide some insight into varying mechanistic pathways nuances myriad help inform future reaction catalyst design.

Language: Английский

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Synergistic Pd/Amine-Catalyzed Stereodivergent Hydroalkylation of 1,3-Dienes with Aldehydes: Reaction Development, Mechanism, and Stereochemical Origins

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(29), P. 10948 - 10962

Published: July 15, 2021

Metal-hydride-catalyzed hydroalkylation of 1,3-dienes with enolizable carbonyl compounds is an atom- and step-economical method for preparing chiral molecules allylic stereocenters. Although high diastereo- enantioselectivities have been achieved many coupling partners, aldehydes not yet used this purpose because they are less stable than other under basic conditions the potential to rapidly epimerize at α-position. Moreover, stereodivergent reactions access complementary diastereomers vicinal stereocenters challenging. Herein, we describe a synergistic palladium/amine catalyst system that allowed us achieve first aldehydes. By choosing appropriate combination palladium amine catalysts, could obtain either syn or anti products, therefore provides highly enantioselective α,β-vicinal Density functional theory calculations revealed mechanism involving PdH formation migratory insertion into alkene, followed by C–C bond formation. The origin stereoselectivities was investigated means distortion/interaction analysis.

Language: Английский

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Synergizing palladium with Lewis base catalysis for stereodivergent coupling of 1,3-dienes with pentafluorophenyl acetates

Chem, Journal Year: 2022, Volume and Issue: 8(10), P. 2784 - 2796

Published: Aug. 17, 2022

Language: Английский

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Enantioselective Intermolecular Pd-Catalyzed Hydroalkylation of Acyclic 1,3-Dienes with Activated Pronucleophiles

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(8), P. 2761 - 2764

Published: Feb. 15, 2018

We report a highly enantioselective Pd-PHOX-catalyzed intermolecular hydroalkylation of acyclic 1,3-dienes. Meldrum's acid derivatives and other activated C-pronucleophiles, such as β-diketones malononitriles, react with variety aryl- alkyl-substituted dienes in ≤20 h at room temperature. The coupled products, obtained up to 96% yield 97.5:2.5 er, are easily transformed into useful chemical building blocks for downstream synthesis.

Language: Английский

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Chiral Pincer Carbodicarbene Ligands for Enantioselective Rhodium-Catalyzed Hydroarylation of Terminal and Internal 1,3-Dienes with Indoles

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(44), P. 15580 - 15583

Published: Oct. 24, 2017

Catalytic enantioselective addition of N-heteroarenes to terminal and internal 1,3-dienes is reported. Reactions are promoted by 5 mol % Rh catalyst supported a new chiral pincer carbodicarbene ligand that delivers allylic substituted arenes in up 95% yield 98:2 er. Mechanistic X-ray evidence presented supports the reaction proceeds via Rh(III)-η3-allyl.

Language: Английский

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Diastereodivergent Synthesis of β‐Amino Alcohols by Dual‐Metal‐Catalyzed Coupling of Alkoxyallenes with Aldimine Esters

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(12), P. 6545 - 6552

Published: Dec. 4, 2020

Abstract Both syn ‐ and anti ‐β‐amino alcohols are common structural motifs in natural products, drug molecules, chiral ligands catalysts. However, the currently available methods for synthesizing these limited to generate only one diastereoisomer. Therefore, development of a unified method stereoselective access complementary diastereomers would be highly desirable. Herein, we report dual‐metal‐catalyzed diastereodivergent coupling alkoxyallenes with aldimine esters. By carefully selecting two metals appropriate ligands, could synthesize both alcohol high enantioselectivity diastereoselectivity from same set starting materials. Furthermore, stereodivergent syntheses all four stereoisomers β‐amino achieved. We demonstrated synthetic utility this by concisely mycestericins F G.

Language: Английский

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CuH-Catalyzed Enantioselective Alkylation of Indole Derivatives with Ligand-Controlled Regiodivergence

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(9), P. 3901 - 3909

Published: Jan. 29, 2019

Enantioenriched molecules bearing indole-substituted stereocenters form a class of privileged compounds in biological, medicinal, and organic chemistry. Thus, the development methods for asymmetric indole alkylation is highly valuable synthesis. Traditionally, achieving N-selectivity reactions significant challenge, since there an intrinsic preference at C3, most nucleophilic position. Furthermore, selective predictable access to either N- or C3-alkylated chiral indoles using catalyst control has been long-standing goal functionalization. Herein, we report ligand-controlled regiodivergent synthesis that relies on polarity reversal strategy. In contrast conventional which are employed as nucleophiles, this transformation employs electrophilic derivatives, N-(benzoyloxy)indoles, coupling partners. prepared with high levels regio- enantioselectivity copper hydride catalyst. The regioselectivity governed by use DTBM-SEGPHOS Ph-BPE supporting ligand. Density functional theory (DFT) calculations conducted elucidate origin regiodivergence.

Language: Английский

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