A Convenient Way for the Conversion of Carboxylic Esters into 2-Substituted Allyl Halides

Kulinkovich, O. G.; Kozyrkov, Yurii Yu.; Bekish, Andrei V.; Matiushenkov, Evgenii A.; Lysenko, Ivan L.

doi:10.1055/s-2004-834869

Cited by 36 publications

(25 citation statements)

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“…环丙醇可以用来合成多种化合物, 比如 β-取代的酮 [10] 、烯丙基氯 [11] 、氮杂环 [12] 以及通过三元环开环的其它化合物, 环丙醇可以被一些单电子氧化剂, 比如过硫酸根和 Ag(I) [13] 、CAN [10] 、锰盐 [12] 等, 氧化开环形成 β-羰基碳自由基. 2013 年 Ilangovan 课题组 [14] 报道了一种 Ref.…”

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Silver-Catalyzed Tandem Radical Cyclization for the Synthesis of 3,3'-Disubstituted Oxindoles

李永红¹,

王君姣²,

魏小红³

et al. 2015

Chin. J. Org. Chem.

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Silver-Catalyzed Tandem Radical Cyclization for the Synthesis of 3,3'-Disubstituted Oxindoles

李永红¹,

王君姣²,

魏小红³

et al. 2015

Chin. J. Org. Chem.

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“…Diethyl ether (Et 2 O) and tetrahydrofuran (THF) were freshly distilled from sodium/benzophenone. Titanium(IV) isopropoxide [Ti(OiPr) 4 ] was purified by distillation, other reagents were used as purchased from commercial suppliers. All reactions were carried out under dry argon.…”

Section: Methodsmentioning

confidence: 99%

“…RMgBr [a] Ti(OiPr) 4 Conditions [b] Yields (%) of products [c] (equiv.) 1a (cis/trans) 3a (11 %) was also detected.…”

Section: Entrymentioning

confidence: 99%

“…Bromide in the Presence of Catalytic Amounts of Ti(OiPr) 4 (Procedure A, Catalytic Mode, Table 1 and Table 3): n-Propylmagnesium bromide (12 mL, 0.9  in Et 2 O or THF, 11 mmol) was slowly added (over 1.5 h) at room temperature to a solution of Ti(OiPr) 4 (0.21 g, 0.75 mmol, 15 mol.%) and methyl butyrate (2a, 0.51 g, 5 mmol) in Et 2 O or THF (10 mL). The brown reaction mixture was stirred for an additional hour, and quenched by careful addition of sulfuric acid (10 %, 10 mL) at 0°C.…”

Section: Cyclopropanation Of Methyl Butyrate (2a) With N-propylmagnesiummentioning

confidence: 99%

“…[1,2] In our studies on the elaboration of a stereoselective method for the preparation of trisubstituted olefins through cationic cyclopropyl-allyl rearrangements of cyclopropyl sulfonates [3,4] we needed to operate with stereochemically pure cis-1,2-dialkylcyclopropanols (cis-1). A toward the reduction of titanium(IV) isopropoxide with Grignard reagents was observed.…”

Section: Introductionmentioning

confidence: 99%

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Advanced Procedure for the Preparation of cis‐1,2‐Dialkylcyclopropanols – Modified Ate Complex Mechanism for Titanium‐Mediated Cyclopropanation of Carboxylic Esters with Grignard Reagents

Kulinkovich¹,

Kananovich²

2007

Eur J Org Chem

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A procedure for the preparation of cis-1,2-dialkylcyclopropanols by titanium(IV) alkoxide-mediated cyclopropanation of carboxylic esters with Grignard reagents, involving the addition of 1.5 equiv. of a higher homologue of ethylmagnesium halide to a mixture of 1 equiv. of carboxylic ester, 1 equiv. of titanium(IV) isopropoxide, and 1.5 equiv. of methylmagnesium halide in ether or tetrahydrofuran at room temperature, has been elaborated. This procedure minimizes the formation of secondary alcohol side products with chromatographic retention factors close to those of the cis-1,2-disubstituted cyclopropanols. Inhibitory action of carboxylic esters

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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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A Convenient Way for the Conversion of Carboxylic Esters into 2-Substituted Allyl Halides

Cited by 36 publications

References 4 publications

Silver-Catalyzed Tandem Radical Cyclization for the Synthesis of 3,3'-Disubstituted Oxindoles

Silver-Catalyzed Tandem Radical Cyclization for the Synthesis of 3,3'-Disubstituted Oxindoles

Advanced Procedure for the Preparation of cis‐1,2‐Dialkylcyclopropanols – Modified Ate Complex Mechanism for Titanium‐Mediated Cyclopropanation of Carboxylic Esters with Grignard Reagents

The Kulinkovich Cyclopropanation of Carboxylic Acid Derivatives

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