Asymmetric synthesis of bicyclo[n.1.0]alkanes by the enantioselective 1,3-CH insertion reaction of chiral magnesium carbenoids

Satoh, Tsuyoshi; Kuramoto, Takayuki; Ogata, Shingo; Watanabe, Hiroyuki; Saitou, Takahito; Tadokoro, Makoto

doi:10.1016/j.tetasy.2009.12.027

Cited by 14 publications

(7 citation statements)

References 25 publications

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“…The partial carbene character of magnesium carbenoids was found to facilitate the nucleophilic substitution at the vinylic and cyclopropyl carbon atoms [5d] . The insertion of magnesium carbenoids into a C–H bond is a powerful method to construct a new C–C bond between an unfunctionalized carbon atom and the carbenoid carbon atom . Previously, we established an efficient method of generating magnesium carbenoids using 1‐chloroalkyl p ‐tolyl sulfoxides as key precursors and found that the resulting magnesium carbenoids inserted into an intramolecular C–H bond to produce cyclopropanes with high efficiency (Scheme ) .…”

Section: Methodsmentioning

confidence: 97%

“…The insertion of magnesium carbenoids into a C–H bond is a powerful method to construct a new C–C bond between an unfunctionalized carbon atom and the carbenoid carbon atom . Previously, we established an efficient method of generating magnesium carbenoids using 1‐chloroalkyl p ‐tolyl sulfoxides as key precursors and found that the resulting magnesium carbenoids inserted into an intramolecular C–H bond to produce cyclopropanes with high efficiency (Scheme ) . DFT calculations of the C–H insertion of magnesium carbenoids would help provide a better understanding of the unusual reactivity of magnesium carbenoids .…”

Section: Methodsmentioning

confidence: 99%

“…The reactivity of metal carbenoids is dependent on the types of metals (Li, Na, Mg, Cu, and Zn) and halogen atoms (Cl, Br, and I) on the carbenoid carbon atom, and the stereochemistry of substrates markedly affects the outcome of the reaction . These experimental results indicate that the C–H insertion does not occur via free carbenes, and that the condition of the C–H bond position (backside of a leaving group) is essential for successful C–H insertion.…”

Section: Methodsmentioning

confidence: 99%

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Mechanism of magnesium carbenoid 1,3-C-H insertion: a DFT study

Kimura

Satoh

2015

J. Phys. Org. Chem.

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The 1,3‐C–H insertion of magnesium carbenoid and related species was investigated via density functional theory (DFT) calculations. The 1,3‐C–H insertion occurred according to an SN2‐like mechanism wherein the nucleophilic C–H bond attacked the electrophilic carbenoid carbon atom. The activation energies for the 1,3‐C–H insertion of (1‐chloropropyl)magnesium chloride, (1‐methoxypropyl)magnesium chloride, and [1‐(methylthio)propyl]magnesium chloride were 20.0, 33.8, and 47.1 kcal/mol, respectively. Copyright © 2015 John Wiley & Sons, Ltd.

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Section: Methodsmentioning

confidence: 97%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Mechanism of magnesium carbenoid 1,3-C-H insertion: a DFT study

Kimura

Satoh

2015

J. Phys. Org. Chem.

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“…172 The reaction was later extended to cycloalkanes from cyclopentane to cyclooctane, and the corresponding products were recovered in 63-83% overall yield and 92-99% ee (Scheme 71). 173 The addition reaction of enolates to vinylsulfoxides was highly stereoselective, leading exclusively to intermediates in which the absolute configuration of the chlorinebearing carbon atom was determined to be S. Then, a sixmembered transition state for the 1,3-CH insertion reaction of the magnesium carbenoid intermediate is envisaged. The sulfoxide-magnesium exchange takes place remarkably with retention of configuration of the sulfinylbearing carbon.…”

Section: C-h Insertionmentioning

confidence: 99%

Asymmetric Cyclopropanation Reactions

2014

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Both physical and organic chemists are interested in the cyclopropane ring, the former owing to the strain inherent to the small ring structure, the latter prompted by the importance of this ring in naturally occurring compounds. In recent years, the increasing interest in enantioselective organic synthesis has led to a large number of papers on the preparation of cyclopropane compounds in enantioenriched form. The last review on asymmetric cyclopropanation reactions is dated 2008, thus an update is necessary with critical comparison of preparations using chiral auxiliaries, chiral metal complexes and organocatalysts. The aim of this review is an overview of these topics from 2008 to mid-2013.

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“…A plausible mechanism of this enantioselective magnesium carbenoid 1,3-CH insertion reaction is proposed as shown in Figure 2. 14…”

Section: -2 13-carbon Hydrogen (13-ch) Insertion Reactionmentioning

confidence: 99%

Recent Advances in the Chemistry and Synthetic Uses of Magnesium Carbenoids

Satoh¹

2012

HETEROCYCLES

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Carbenes and carbenoids have long been recognized to be a highly reactive species and are frequently used as intermediates in organic synthesis.However, most of the carbenes and carbenoids are relatively short-lived and are too reactive to control. Recently, the author's group found that the treatment of aryl -chloroalkyl sulfoxides and -chlorovinyl p-tolyl sulfoxides with a Grignard reagent at low temperature gave magnesium carbenoids via the sulfoxide-magnesium exchange reaction. Magnesium carbenoids, cyclopropylmagnesium carbenoids, cyclobutylmagnesium carbenoids, magnesium alkylidene carbenoids, and magnesium -oxido carbenoids were generated from the corresponding -chloro sulfoxides with a Grignard reagent at low temperature.The generated magnesium carbenoids were proved to be relatively stable and they showed very interesting reactivity with several nucleophiles to afford many unprecedented new reactions. The present review is written for the purpose of reflecting recent achievements in the areas of chemistry and synthetic application of above-mentioned magnesium carbenoids. This review mainly covers literature from 2006 to late 2011. CONTENTS1.

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Asymmetric synthesis of bicyclo[n.1.0]alkanes by the enantioselective 1,3-CH insertion reaction of chiral magnesium carbenoids

Cited by 14 publications

References 25 publications

Mechanism of magnesium carbenoid 1,3-C-H insertion: a DFT study

Mechanism of magnesium carbenoid 1,3-C-H insertion: a DFT study

Asymmetric Cyclopropanation Reactions

Recent Advances in the Chemistry and Synthetic Uses of Magnesium Carbenoids

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