A Michael Addition-Induced Favorskii Rearrangement

Tsuboi, Sadao; Nagae, Hiroyuki; Yamato, Hirofumi; Takeda, Akira

doi:10.1246/bcsj.60.836

Cited by 7 publications

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

Favorskii Rearrangement

2010

Comprehensive Organic Name Reactions and Reagents

View full text Add to dashboard Cite

The Favorskii rearrangement is a base‐induced rearrangement of α‐halo ketones to the corresponding carboxylic acid derivatives (e.g., acids, esters, and amides) with the same number of carbon atoms in the skeletons; and the bases can be hydroxide, alkoxide, or amines. There have been at least six different mechanisms presented for this rearrangement. Among these mechanisms, the semibenzilic acid mechanism and cyclopropanone mechanisms are most plausible. Besides this, many experimental results have shown that the actual reaction mechanisms depend on the reaction conditions. This reaction has wide application for the synthesis of highly strained esters, bicyclic esters, some steroids, etc.

show abstract

Favorskii Rearrangement

2010

Comprehensive Organic Name Reactions and Reagents

View full text Add to dashboard Cite

show abstract

Ring Contraction Reactions in the Total Synthesis of Biologically Active Natural Products

Silva

2013

Stereoselective Synthesis of Drugs and Natural Products

View full text Add to dashboard Cite

Strategic reactions in synthetic organic chemistry are those that increase the molecular complexity of the starting material. Particularly important are the transformations where new carbon–carbon bonds are formed. Although during a ring contraction the number of carbon–carbon bonds is conserved, the reorganization of the skeleton may occur with a high level of selectivity leading to a product not easily accessed by other methods. Even highly strained systems can be obtained using the Favorskii and Wolff rearrangements. Additionally, a ring contraction approach opens new applications for the chiral pool and for readily available starting materials. This chapter presents ring contraction reactions as an efficient tool in the stereoselective synthesis of biologically active natural products. The reactions discussed are Favorskii rearrangement, oxidative rearrangements, Wolff rearrangement, thermolysis of aryliodonium ylides, and rearrangements through cationic and radical intermediates.

show abstract

ChemInform Abstract: A Michael Addition‐Induced Favorskii Rearrangement.

et al. 1987

View full text Add to dashboard Cite

090ChemInform Abstract The reaction of 6-chloro-2-isopropylidenecyclohexanone (Ia) with NaOMe affords the product (IIa), which results by simple substitution, and the methyl 2-isopropylidene-1-cyclopentanecarboxylate (IIIa) as the main product along with the methyl trans-(1-methoxy-1-methylethyl)-1-cyclopentanecarboxylate (IVa). The products (IIIa) and (IVa) are formed by Favorskii rearrangements of the cyclohexane skeleton. These rearrangements are started by a Michael addition of NaOMe to the carbon-carbon double bond of (Ia). The analogous reactions of 2-ethylidene-(Ib) or 2-benzylidene-6-chlorocyclohexanone (Ic) with NaOMe afford the products (IVb) -erythro:threo = 20:18 -and (Vb) or (IVc) -erythro:threo = 33:29 -and (VIc), which are all formed by Michael addition-induced Favorskii rearrangements.

show abstract

A Michael Addition-Induced Favorskii Rearrangement

Abstract: Reaction of 6-chloro-2-vinylidenecyclohexanone with sodium methoxide gave methyl 2-vinylidene-1-cyclopentanecarboxylate and methyl trans-2-(1-methoxyalkyl)-1-cyclopentanecarboxylate along with 6-methoxy-2-vinylidenecyclohexanone via a Michael addition-induced Favorskii rearrangement.

Cited by 7 publications

References 18 publications

Favorskii Rearrangement

Favorskii Rearrangement

Ring Contraction Reactions in the Total Synthesis of Biologically Active Natural Products

ChemInform Abstract: A Michael Addition‐Induced Favorskii Rearrangement.

Contact Info

Product

Resources

About