Synthesis and properties of 3,4-di-t-butylbutanedione

Groot, Ae. de; Oudman, D.; Wynberg, Hans

doi:10.1016/s0040-4039(01)87936-3

Cited by 15 publications

(2 citation statements)

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“…Hence, in agreement with experimental observations [5–7], cyclobutane-1,2-dione is calculated to react via benzilic acid rearrangement to the ring-contracted product, i.e., 1-hydroxycyclopropanecarboxylate ( 2 ).…”

Section: Resultssupporting

confidence: 86%

“…The benzilic acid rearrangement of cyclic 1,2-diones [3–4] leads to ring contraction, e.g., the rearrangement of cyclobutane-1,2-dione ( 1 ) to 1-hydroxycyclopropanecarboxylate ( 2 ) [5–7]. In contrast, cyclobut-3-ene-1,2-diones 3 react to 2-oxobut-3-enoates 4 (at least formally according to path B) [8], whereas benzocyclobutene-1,2-diones 5 lead to 2-formylbenzoates 6 (path C, Scheme 2) [9].…”

Section: Introductionmentioning

confidence: 99%

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A computational study of base-catalyzed reactions of cyclic 1,2-diones: cyclobutane-1,2-dione

Sultana¹,

Fabian²

2013

Beilstein J. Org. Chem.

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SummaryThe reaction of cyclobutane-1,2-dione with hydroxide was studied by a variety of ab initio (MP2, SCS-MP2, CCSD(T), CEPA/1) and density functional (M06-2X) methods. Three possible reaction paths of the initially formed tetrahedral adduct leading to either 1-hydroxycyclopropane-1-carboxylate (benzilic acid type rearrangement, path A), α-oxobutanoate (path B) or γ-oxobutanoate (path C) were considered. Although the latter two products show similar or even more negative Gibbs free energies of reaction than calculated for the benzilic acid type rearrangement, the Gibbs free energies of activation are substantially higher. According to the calculations, the only feasible reaction appears to be the formation of 1-hydroxycyclopropane-1-carboxylate, which is corroborated by previous experimental observations.

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Section: Resultssupporting

confidence: 86%

Section: Introductionmentioning

confidence: 99%

A computational study of base-catalyzed reactions of cyclic 1,2-diones: cyclobutane-1,2-dione

Sultana¹,

Fabian²

2013

Beilstein J. Org. Chem.

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The Acyloin Condensation

2011

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The acyloin condensation usually involves the reductive dimerization of a carboxylic ester, although acid chlorides and the anhydrides have been used. The reducing agent is in an alkali metal and the product is an ene‐diolate. Two gram‐atoms of metal are required for each mole of ester with the concomitant formation of a mole of akoxide and one‐half mole of the ene‐diolate. Oxidation of acyloins to diketoes can be accomplished by a variety of reagents. Acyloins can be reduced to ketones by various modifications of the Clemmenson technique. Under mild conditions the ketone will dominate. This chapter presents a complete picture of both the linear and cyclic acyloin condensation with particular emphasis on developments since 1960. The discussion is closely limited to the acyloin condensation and its modifications.

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The Kulinkovich Cyclopropanation of Carboxylic Acid Derivatives

Kun

Kulinkovich

2012

Organic Reactions

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Cyclopropanes are characterized by high ring‐strain energy and have been employed as useful building blocks in organic synthesis. The incorporation of a heteroatom donor substituent such as OH, OR, NR2, or SR on the ring imparts enhanced reactivity. Hydroxycyclopropanes (cyclopropanols) in particular have been thoroughly studied due to their facile ring cleavage. Among several known methods, a new method for preparation of cyclopropanols involves dialkoxytitanacyclopropane‐mediated cyclopropanation (the Kulinkovich cyclopropanation) of esters with Grignard reagent in the presence of titanium isopropoxide. The striking feature of this method is the facile formation of a three‐membered ring from a simple Grignard reagent which acts as a 1,2‐dicarbanion equivalent through a pivotal dialkoxytitana‐cycloproapne intermediate. These reactions benefit from the availability of inexpensive reagents, ease of operation, and high selectivity for cis ‐dialkylcyclopropanols. This cyclopropanation reaction has since been extended to other carboxylic derivatives to provide convenient access to several heteroatom‐substituted cyclopropanes. The objective of this chapter is to provide an updated, comprehensive coverage of the literature on the Kulinkovich cyclopropanation reaction and related processes. Key mechanistic issues are summarized.

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Synthesis and properties of 3,4-di-t-butylbutanedione

Cited by 15 publications

References 9 publications

A computational study of base-catalyzed reactions of cyclic 1,2-diones: cyclobutane-1,2-dione

A computational study of base-catalyzed reactions of cyclic 1,2-diones: cyclobutane-1,2-dione

The Acyloin Condensation

The Kulinkovich Cyclopropanation of Carboxylic Acid Derivatives

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