Asymmetric Copper‐Catalyzed Vinylogous Mukaiyama Michael Addition of Cyclic Dienol Silanes to Unsaturated α‐Keto Phosphonates

Steinkamp, Anne‐Dorothee; Frings, Marcus; Thomé, Isabelle; Schiffers, Ingo; Bolm, Carsten

doi:10.1002/chem.201500861

Cited by 24 publications

(7 citation statements)

References 65 publications

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“…A similar catalytic system was also exploited by Bolm and co-workers in 2015 for the synthesis of valuable enantioenriched, phosphorus-containing compounds through an asymmetric Cu(II)-catalyzed VMMcR between differently substituted cyclic dienol silanes 739 and α,β-unsaturated α-keto phosphonates 740 (Scheme , eq 2) …”

Section: Vinylogous Esters and Lactonesmentioning

confidence: 89%

“…A similar catalytic system was also exploited by Bolm and coworkers in 2015 for the synthesis of valuable enantioenriched, phosphorus-containing compounds through an asymmetric Cu(II)-catalyzed VMMcR between differently substituted cyclic dienol silanes 739 and α,β-unsaturated α-keto phosphonates 740 (Scheme 190, eq 2). 493 Using the combination of the commercially available C 2symmetric bisoxazoline ligand L24 with copper(II) perchlorate hexahydrate salt [Cu(ClO 4 ) 2 •6H 2 O], the VMMcR of 739 and 740 provided a variety of γ-homologated butenolides 741 in moderate to high yields (up to 82%) and high stereoselectivities (up to 99:1 dr and up to 98% ee). Of note, when the 4-methoxy-furan derivative was used as the nucleophilic partner, a different chemoselectivity was observed, providing the 1,2 aldol adduct instead of the 1,4, in a low 22% yield, 2.3:1 dr, and 97% ee (not shown).…”

Section: Additions To Cn Bondsmentioning

confidence: 99%

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New Developments of the Principle of Vinylogy as Applied to π-Extended Enolate-Type Donor Systems

et al. 2020

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The principle of vinylogy states that the electronic effects of a functional group in a molecule are possibly transmitted to a distal position through interposed conjugated multiple bonds. As an emblematic case, the nucleophilic character of a π-extended enolate-type chain system may be relayed from the legitimate α-site to the vinylogous γ, ε, ..., ω remote carbon sites along the chain, provided that suitable HOMO-raising strategies are adopted to transform the unsaturated pronucleophilic precursors into the reactive polyenolate species. On the other hand, when “unnatural” carbonyl ipso -sites are activated as nucleophiles (umpolung), vinylogation extends the nucleophilic character to “unnatural” β, δ, ... remote sites. Merging the principle of vinylogy with activation modalities and concepts such as iminium ion/enamine organocatalysis, NHC-organocatalysis, cooperative organo/metal catalysis, bifunctional organocatalysis, dicyanoalkylidene activation, and organocascade reactions represents an impressive step forward for all vinylogous transformations. This review article celebrates this evolutionary progress, by collecting, comparing, and critically describing the achievements made over the nine year period 2010–2018, in the generation of vinylogous enolate-type donor substrates and their use in chemical synthesis.

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Section: Vinylogous Esters and Lactonesmentioning

confidence: 89%

Section: Additions To Cn Bondsmentioning

confidence: 99%

New Developments of the Principle of Vinylogy as Applied to π-Extended Enolate-Type Donor Systems

et al. 2020

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“…Bolm and co-workers found that the complex L47 –Cu(ClO 4 ) 2 was an efficient catalyst for the ACA of siloxy furans to unsaturated α-keto phosphonates (Scheme a) . The position of the methyl group on the siloxy furans played a significant role in the reaction, especially on the reactivity.…”

Section: C–c Bond Formation By Metal-catalyzed Aca Reactionsmentioning

confidence: 99%

“…Bolm and co-workers found that the complex L47− Cu(ClO 4 ) 2 was an efficient catalyst for the ACA of siloxy furans to unsaturated α-keto phosphonates (Scheme 61a). 264 The position of the methyl group on the siloxy furans played a significant role in the reaction, especially on the reactivity. While an 82% yield with 98% ee was achieved for the 3methyl-substituted siloxy furans, the 4-or 5-substituted siloxy furans gave only 56% yield with 91% ee, and 27% yield with 70% ee, respectively, under the same conditions.…”

Section: Conjugate Addition Of Vinylogous Nucleophiles and Indolesmentioning

confidence: 99%

Recent Advances in Metal-Catalyzed Asymmetric 1,4-Conjugate Addition (ACA) of Nonorganometallic Nucleophiles

2018

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The metal-catalyzed asymmetric conjugate addition (ACA) reaction has emerged as a general and powerful approach for the construction of optically active compounds and is among the most significant and useful reactions in synthetic organic chemistry. In recent years, great progress has been made in this area with the use of various chiral metal complexes based on different chiral ligands. This review provides comprehensive and critical information on the enantioselective 1,4-conjugate addition of nonorganometallic (soft) nucleophiles and their importance in synthetic applications. The literature is covered from the last 10 years, and a number of examples from before 2007 are included as background information. The review is divided into multiple parts according to the type of nucleophile involved in the reaction (such as C-, B-, O-, N-, S-, P-, and Si-centered nucleophiles) and metal catalyst systems used.

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“…The system comprising 10 mol % Cu(ClO 4 ) 2 ·6H 2 O and 10 mol % bisoxazoline ligand L11 proved to be an efficient catalyst for this enantioselective conjugate addition delivering phosphonate-containing γ-butenolides 81 with high stereoselectivity in an anti fashion ( Scheme 38 ). 106 …”

Section: Furanone-derived Enolates As Nucleophilesmentioning

confidence: 99%

Catalytic Asymmetric Synthesis of Butenolides and Butyrolactones

2017

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γ-Butenolides, γ-butyrolactones, and derivatives, especially in enantiomerically pure form, constitute the structural core of numerous natural products which display an impressive range of biological activities which are important for the development of novel physiological and therapeutic agents. Furthermore, optically active γ-butenolides and γ-butyrolactones serve also as a prominent class of chiral building blocks for the synthesis of diverse biological active compounds and complex molecules. Taking into account the varying biological activity profiles and wide-ranging structural diversity of the optically active γ-butenolide or γ-butyrolactone structure, the development of asymmetric synthetic strategies for assembling such challenging scaffolds has attracted major attention from synthetic chemists in the past decade. This review offers an overview of the different enantioselective synthesis of γ-butenolides and γ-butyrolactones which employ catalytic amounts of metal complexes or organocatalysts, with emphasis focused on the mechanistic issues that account for the observed stereocontrol of the representative reactions, as well as practical applications and synthetic potentials.

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Asymmetric Copper‐Catalyzed Vinylogous Mukaiyama Michael Addition of Cyclic Dienol Silanes to Unsaturated α‐Keto Phosphonates

Cited by 24 publications

References 65 publications

New Developments of the Principle of Vinylogy as Applied to π-Extended Enolate-Type Donor Systems

New Developments of the Principle of Vinylogy as Applied to π-Extended Enolate-Type Donor Systems

Recent Advances in Metal-Catalyzed Asymmetric 1,4-Conjugate Addition (ACA) of Nonorganometallic Nucleophiles

Catalytic Asymmetric Synthesis of Butenolides and Butyrolactones

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