Asymmetric synthesis of all-carbon quaternary spirocycles via a catalytic enantioselective allylic alkylation strategy

Shockley, Samantha E.; Hethcox, J. Caleb; Stoltz, Brian M.

doi:10.1016/j.tetlet.2017.07.022

Cited by 7 publications

(4 citation statements)

References 29 publications

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“…Stoltz and co-workers developed the DAAA of cyclic ketone substrates containing a masked methyl vinyl ketone at the α-position ( Scheme 230 ). 609 The dioxin unit in 171 was employed as a surrogate for bromomethyl vinyl ketone 172 to overcome problems associated with nucleophilic addition to 172 . The Pd catalyst derived from p -(CF 3 ) 3 - t -Bu-PHOX ligand L122 ( Scheme 208 ) enabled the preparation of α-allylated products with high enantioselectivities (up to 99% ee ).…”

Section: Asymmetric Decarboxylative Allylic Substitutionmentioning

confidence: 99%

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

410

202

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This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution and decarboxylative and oxidative allylic substitutions. For each reaction, the catalytic data, as well as examples of their application to the synthesis of more complex molecules, are collected. Sections in which we discuss key mechanistic aspects for high selectivity and a comparison with other metals (with advantages and disadvantages) are also included. For Pd-catalyzed asymmetric allylic substitution, the catalytic data are grouped according to the type of nucleophile employed. Because of the prominent position of the use of stabilized carbon nucleophiles and heteronucleophiles, many chiral ligands have been developed. To better compare the results, they are presented grouped by ligand types. Pd-catalyzed asymmetric decarboxylative reactions are mainly promoted by PHOX or Trost ligands, which justifies organizing this section in chronological order. For asymmetric oxidative allylic substitution the results are grouped according to the type of nucleophile used.

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Section: Asymmetric Decarboxylative Allylic Substitutionmentioning

confidence: 99%

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

410

202

View full text Add to dashboard Cite

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“…For the synthesis of spirocycles, a 4H-1,3-dioxin moiety 23 was used as a surrogate for a vinyl ketone. [84] Allylated product 24 could be converted into spirocycle 25 in excellent yield via thermal cleavage of the dioxin moiety followed by ring closing metathesis using Hoveyda-Grubbs II catalyst (HG-II) (Scheme 53). [85] For the formal synthesis of (À )-platencin, Stoltz and coworkers used a cyclohexanone-derived β-ketoester for the construction of the quaternary center via decarboxylative allylation, followed by cyclization in order to build the bicyclic framework of the natural product.…”

Section: Decarboxylative Allylic Alkylations Of Cyclic Ketonesmentioning

confidence: 99%

“…For the synthesis of spirocycles, a 4 H ‐1,3‐dioxin moiety 23 was used as a surrogate for a vinyl ketone [84] . Allylated product 24 could be converted into spirocycle 25 in excellent yield via thermal cleavage of the dioxin moiety followed by ring closing metathesis using Hoveyda‐Grubbs II catalyst (HG‐II) (Scheme 53).…”

Section: Decarboxylative Allylic Alkylationsmentioning

confidence: 99%

The Allylic Alkylation of Ketone Enolates

Junk

Kazmaier

2020

ChemistryOpen

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The palladium‐catalyzed allylic alkylation of non‐stabilized ketone enolates was thought for a long time to be not as efficient as the analogous reactions of stabilized enolates, e. g. of malonates and β‐ketoesters. The field has experienced a rapid development during the last two decades, with a range of new, highly efficient protocols evolved. In this review, the early developments as well as current methods and applications of palladium‐catalyzed ketone enolate allylations will be discussed.

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“…The Stoltz group reported the DAAA of cyclic ketone substrates bearing a masked methyl vinyl ketone at the α‐position (Scheme ) . The dioxin group in 123 was used as a surrogate for bromomethyl vinyl ketone 122 to circumvent problems with nucleophilic addition to 122 .…”

Section: Development Of Palladium‐catalyzed Decarboxylative Asymmetrimentioning

confidence: 99%

Palladium‐Catalyzed Decarboxylative Asymmetric Allylic Alkylation: Development, Mechanistic Understanding and Recent Advances

2019

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The palladium‐catalyzed decarboxylative asymmetric allylic alkylation (DAAA) is comprehensively reviewed, from its original development to recent advances in terms of substrate scope, reactivity, regio‐ and enantioselectivity. The current understanding of the mechanistic details, based on a combination of experimental and computational studies, is described. Selected examples of the application of this asymmetric synthetic methodology in natural product synthesis are given. The exploration of Pd‐catalyzed decarboxylative asymmetric catalysis, in particular, the related interceptive decarboxylative asymmetric allylic alkylation, has become a focus in recent years and this is also summarized.

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Asymmetric synthesis of all-carbon quaternary spirocycles via a catalytic enantioselective allylic alkylation strategy

Cited by 7 publications

References 29 publications

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

The Allylic Alkylation of Ketone Enolates

Palladium‐Catalyzed Decarboxylative Asymmetric Allylic Alkylation: Development, Mechanistic Understanding and Recent Advances

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