Very Recent Advances in Vinylogous Mukaiyama Aldol Reactions and Their Applications to Synthesis

It is a challenging objective in synthetic organic chemistry to create efficient access to biologically active compounds. In particular, one structural element which is frequently incorporated into the framework of complex natural products is a β-hydroxy ketone. In this context, the aldol reaction is the most important transformation to generate this structural element as it not only creates new C–C bonds but also establishes stereogenic centers. In recent years, a large variety of highly selective methodologies of aldol and aldol-type reactions have been put forward. In this regard, the vinylogous Mukaiyama aldol reaction (VMAR) became a pivotal transformation as it allows the synthesis of larger fragments while incorporating 1,5-relationships and generating two new stereocenters and one double bond simultaneously. This review summarizes and updates methodology-oriented and target-oriented research focused on the various aspects of the vinylogous Mukaiyama aldol (VMA) reaction. This manuscript comprehensively condenses the last four years of research, covering the period 2016–2019.

• Publication year

  2019

• Venue

  Molecules

• Publication date

  2019-08-22

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.3390/molecules24173040PMID 31443344PMCID 6749529
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Total Synthesis of PF1163B

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  2019influential reference
• Stereoselective Synthesis of 2,3,5-Trisubstituted Tetrahydrofurans Initiated by a Titanium-BINOLate-Catalyzed Vinylogous Aldol Reaction.

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• Development and Application of Asymmetric Organocatalytic Mukaiyama and Vinylogous Mukaiyama-Type Reactions.

  2018cited by this paper
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  2018influential reference
• Recent development of vinylogous Mukaiyama aldol reactions

  2018cited by this paper
• Asymmetric vinylogous Mukaiyama aldol reaction of isatins under bifunctional organocatalysis: enantioselective synthesis of substituted 3-hydroxy-2-oxindoles.

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  2017cited by this paper
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  2017cited by this paper
• Total Synthesis of the Proposed Structure of Maltepolide C.

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  2016influential reference
• Concise Total Synthesis of Nannocystin A.

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• Total Synthesis of Aetheramide A.

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  2014cited by this paper
• The vinylogous Mukaiyama aldol reaction (VMAR) in natural product synthesis.

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• Syn‐Selective Kobayashi Aldol Reaction Using the E,E‐Vinylketene Silyl N,O‐Acetal.

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• The impact of the Mukaiyama aldol reaction in total synthesis.

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• Syn-selective Kobayashi aldol reaction using the E,E-vinylketene silyl N,O-acetal.

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  2010influential reference
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• Lewis base activation of Lewis acids: catalytic, enantioselective vinylogous aldol addition reactions.

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• Recent Advances in Vinylogous Aldol Reactions and Their Applications in the Syntheses of Natural Products

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• Catalytic, enantioselective, vinylogous aldol reactions.

  2005cited by this paper
• Lewis base activation of Lewis acids: catalytic, enantioselective addition of silyl ketene acetals to aldehydes.

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• Remote asymmetric induction with vinylketene silyl n,o-acetal.

  2004influential reference
• Recent Advances in Asymmetric Aldol Reaction of Masked Acetoacetic Esters Promoted by Ti(IV)/BINOL. A New Methodology, Non-Linear Effects and Autoinduction

  2004cited by this paper
• Lewis base activation of Lewis acids. Vinylogous aldol reactions.

  2003cited by this paper
• Catalytic, enantioselective aldol additions to ketones.

  2002cited by this paper
• Catalytic asymmetric access to alpha,beta unsaturated delta-lactones through a vinylogous aldol reaction: application to the total synthesis of the Prelog-Djerassi lactone.

  2001cited by this paper
• Catalytic Asymmetric Access to α,β Unsaturated δ-Lactones through a Vinylogous Aldol Reaction: Application to the Total Synthesis of the Prelog-Djerassi Lactone

  2001cited by this paper
• The vinylogous aldol reaction: a valuable, yet understated carbon-carbon bond-forming maneuver.

  2000cited by this paper
• C2-Symmetric Copper(II) Complexes as Chiral Lewis Acids. Scope and Mechanism of the Catalytic Enantioselective Aldol Additions of Enolsilanes to Pyruvate Esters

  1999cited by this paper
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  1999cited by this paper
• Mechanistic Insights into Cu-Catalyzed Asymmetric Aldol Reactions: Chemical and Spectroscopic Evidence for a Metalloenolate Intermediate.

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  1998cited by this paper
• Apparent Catalytic Generation of Chiral Metal Enolates: Enantioselective Dienolate Additions to Aldehydes Mediated by Tol-BINAP·Cu(II) Fluoride Complexes

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  1995cited by this paper
• Catalytic, Enantioselective Dienolate Additions to Aldehydes: Preparation of Optically Active Acetoacetate Aldol Adducts

  1995cited by this paper
• Use of 1, 3-Dioxin-4-ones and Related Compounds in Synthesis. XLIV. Asymmetric Aldol Reaction of 4-Trimethylsiloxy-6-methylene-1, 3-dioxines : Use of Tartaric Acid-Derived (Acyloxy)borane Complex as the Catalyst

  1994cited by this paper
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  1992cited by this paper
• Silicon-directed aldol condensation. Evidence for a pseudorotational mechanism

  1992cited by this paper
• A Silicon‐Directed Aldol Condensation. Synthesis of Enantiomerically Pure Anti Aldols.

  1991cited by this paper
• A silicon-directed aldol condensation. Synthesis of enantiomerically pure anti aldols

  1990cited by this paper
• A New Method for the Preparation of δ-Alkoxy-α,β-unsaturated Aldehydes and Polyenals

  1977cited by this paper
• NEW METHOD FOR THE PREPARATION OF POLYENALS FROM δ-ALKOXY-α,β-UNSATURATED ALDEHYDES

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• Molecular Orbital Theory of Orientation in Aromatic, Heteroaromatic, and Other Conjugated Molecules

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• The Principle of Vinylogy.

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• A Straightforward Synthesis of Polyketides via Ester Dienolate Matteson Homologation

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• Water plays a crucial role: Small molecule catalyzed C–C/C–X bond forming reactions using organosilicon reagents under “wet” conditions

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• Condensation Reaction

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• Editorial to the Special Issue “Total Synthesis of Natural Products: A Themed Issue Dedicated to Professor Dr. Dieter Schinzer for His 65th Birthday”

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