Palladium-catalyzed diastereoselective synthesis of homoaldol equivalent products

Horino, Yoshikazu; Sugata, Miki; Sugita, Tetsu; Aimono, Ataru; Abe, Hitoshi

doi:10.1016/j.tetlet.2017.04.064

Cited by 4 publications

(3 citation statements)

References 71 publications

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“…During ligand screening, the Pd(OAc) 2 /P(4-MeOC 6 H 4 ) 3 catalyst system afforded 4aaa in 73% yield with high ( Z )-stereoselectivity (entries 4–6). The homoaldol equivalent product 6aa did not react with 3a to provide 4aaa under the Pd(OAc) 2 /P(4-MeOC 6 H 4 ) 3 catalyst system. In addition, isomerization of ( Z )- 4aaa to ( E )- 4aaa was not observed under the reaction conditions.…”

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confidence: 99%

Controllable Stereoselective Synthesis of (Z)- and (E)-Homoallylic Alcohols Using a Palladium-Catalyzed Three-Component Reaction

et al. 2017

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Diastereoselective synthesis of (Z)- and (E)-homoallylic alcohols using a Pd-catalyzed three-component reaction of 3-(pinacolatoboryl)allyl benzoates, aldehydes, and aryl stannanes was developed, which provides an alternative method for the allylboration of aldehydes using α,γ-diaryl-substituted allylboronates. Both sets of reaction conditions enable access to either (Z)- or (E)-homoallylic alcohols with good to high alkene stereocontrol. The present method showed good functional group compatibility and generality. Efficient chirality transfer reactions to afford enantioenriched (Z)- and (E)-homoallylic alcohols were also achieved.

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confidence: 99%

Controllable Stereoselective Synthesis of (Z)- and (E)-Homoallylic Alcohols Using a Palladium-Catalyzed Three-Component Reaction

et al. 2017

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“…The palladium‐catalyzed nucleophilic allylation of aldehydes using B(pin)‐substituted allyl acetates was initially examined (Scheme 16). [39] This method was applicable to various aldehydes to produce ( Z )‐ anti ‐homoaldol equivalent products together with a non‐negligible amount of ( E )‐cinnamyl acetate as the by‐product (0–18 %). In some cases, switching the ligand from Xantphos to ( p ‐CF 3 C 6 H 4 ) 3 P improved the chemical yield.…”

Section: Palladium‐catalyzed Nucleophilic Allylation Of Aldehydesmentioning

confidence: 99%

Versatile Reactivity of Metalloid‐Substituted π‐Allylpalladium Species

Horino

Korenaga

2021

The Chemical Record

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π-Allylpalladium complexes can not only serve as electrophilic allylating agents for a broad range of nucleophiles, but also nucleophilic allylating agents for electrophiles depending on their electronic environments. In contrast to these typical reactivities of π-allylpalladium complexes, silylated and borylated π-allylpalladium species show unique reactivities that can allow versatile transformations in addition to simple allylation. Herein, four different types of transformations that are in principle achieved via the inherently reactive silylated and borylated π-allylpalladium species as common intermediates are described. An appropriate selection of ligands of the silylated and borylated π-allylpalladium species can allow control over the reaction pathways.

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“…To address the racemization process, we envisioned that a competing reaction involving palladium‐catalyzed alkene isomerization of ( R )‐ 2 a followed by allylboration of benzaldehyde may also occur [27a] if the palladium‐catalyzed coupling of homoaldol equivalent 5 with 3 a is feasible (Scheme 3a). This is because homoaldol equivalent 5 is known to be produced in its racemic form [27b] . To test this hypothesis, we examined the reaction between rac ‐ 2 a and 1 a in the absence of 3 a (Scheme 3b).…”

Section: Methodsmentioning

confidence: 99%

Palladium‐Catalyzed Diastereoselective Synthesis of (Z)‐Conjugated Enynyl Homoallylic Alcohols

et al. 2021

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The diastereoselective synthesis of antihomoallylic alcohols bearing conjugated (Z)-enynes through a palladium-catalyzed three-component reaction is described. This reaction features a broad substrate scope, good functional group compatibility, and high levels of (Z)-alkene stereocontrol. In this reaction, Pd(0) functions as a catalyst in two fundamental steps of the tandem sequence: 1) the generation of a borylated π-allylpalladium species from bifunctional conjunctive reagents, inducing umpolung allylation of aldehydes, and 2) C(sp 2 )À C-(sp) cross-coupling. Further transformations of the obtained products highlight their synthetic utility.

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Palladium-catalyzed diastereoselective synthesis of homoaldol equivalent products

Cited by 4 publications

References 71 publications

Controllable Stereoselective Synthesis of (Z)- and (E)-Homoallylic Alcohols Using a Palladium-Catalyzed Three-Component Reaction

Controllable Stereoselective Synthesis of (Z)- and (E)-Homoallylic Alcohols Using a Palladium-Catalyzed Three-Component Reaction

Versatile Reactivity of Metalloid‐Substituted π‐Allylpalladium Species

Palladium‐Catalyzed Diastereoselective Synthesis of (Z)‐Conjugated Enynyl Homoallylic Alcohols

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