New Family of Cyclopropanating Reagents: Synthesis, Reactivity, and Stability Studies of Iodomethylzinc Phenoxides

Charette, André B.; Francoeur, S.; Martel, Jonathan; Wilb, Nicole

doi:10.1002/1521-3773(20001215)39:24<4539::aid-anie4539>3.0.co;2-9

Cited by 79 publications

(10 citation statements)

References 24 publications

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“…The pioneering works of Simmons and Smith have revealed the rich potential of zinc carbenoids in the synthesis of cyclopropane compounds and gave a powerful impetus to the development of new cyclopropanating agents . Due to the use of readily available precursors and reagents as well as the simplicity of the procedure, the so‐called Simmons–Smith reaction and its analogues became extremely popular.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Spiro[2.2]pentanes and Spiro[2.3]hexanes Employing the Me₃Al/CH₂I₂ Reagent

et al. 2017

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Substituted alkylidenecyclopropanes reacted with 5 equivalents each of Me3Al and CH2I2 at room temperature in hexane to give 1‐mono‐ and 1,1‐disubstituted spiro[2.2]pentanes in high yields. Surprisingly, the same reaction with substituted alkylidenecyclopropanes in CH2Cl2 afforded exclusively 1,1‐disubstituted spiro[2.3]hexanes. The transformation of 1,1‐diphenylspiro[2.2]pentane into 1,1‐diphenylspiro[2.3]hexane was studied with the use of CD2I2 and a plausible mechanism was suggested. The reaction of substituted alkylidenecyclobutanes with the Me3Al/CH2I2 reagent in CH2Cl2 gave only 1,1‐disubstituted spiro[2.3]hexanes.

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Section: Introductionmentioning

confidence: 99%

Synthesis of Spiro[2.2]pentanes and Spiro[2.3]hexanes Employing the Me₃Al/CH₂I₂ Reagent

et al. 2017

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“…Deprotection of the 4‐OH group34 set the stage for the OH‐directed cyclopropanation of homoallylic alcohol 15 , which, as expected, required a longer reaction time than what is usually required for allylic alcohols, such as, for example, in the preparation of 1 35. We first investigated the use of Charette’s zinc carbenoid (2,4,6‐Cl 3 C 6 H 2 OZnCH 2 I)36 with alcohol 15 , but the reaction was sluggish at room temperature and never reached completion. Despite the low conversion rate, we were glad to observe that the hydroxy group still exerted a complete stereocontrol, thus leading to the cis ‐isomer 2 a only (see below).…”

Section: Resultsmentioning

confidence: 99%

Cyclopropane Pipecolic Acids as Templates for Linear and Cyclic Peptidomimetics: Application in the Synthesis of an Arg‐Gly‐Asp (RGD)‐Containing Peptide as an α_vβ₃ Integrin Ligand

Sernissi¹,

Petrović²,

Scarpi³

et al. 2014

Chemistry A European J

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The synthesis and evaluation of substituted cyclopropane pipecolic acids (CPA) as conformationally restricted templates for linear and cyclic peptidomimetics is reported. A variety of differently substituted (poly)hydroxy- and amino-2-azabicyclo[4.1.0]heptane-1-carboxylic acids were prepared by means of the Pd-catalyzed methoxycarbonylation of suitably functionalized lactam-derived enol phosphates, followed by OH-directed cyclopropanation. CPAs were successfully introduced into a linear peptide sequence to assess the cis/trans isomerism about the pipecolic acid peptide bond, and in a cyclic peptidomimetic that bore the Arg-Gly-Asp (RGD) sequence, which displayed nanomolar activity as antagonist of the αvβ3 integrin in M21 human melanoma cells. Thus, CPAs appear to be suitable for the generation of novel peptidomimetics for drug discovery.

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“…First, the use of zinc carbenoid species with different electronic properties was studied (Table ). It is known that electron withdrawing additives, such as CF 3 CO 2 H, CF 3 CH 2 OH, and phenol derivatives, can generate more reactive zinc carbenoids of the type Y–ZnCH 2 I (Y is the conjugate base of the acids listed above). Marginal improvement in the cyclopropanation conversion was observed, in particular with use of CF 3 CH 2 OH (entry 2).…”

Section: Resultsmentioning

confidence: 99%

Tandem catalytic enantio‐ and diastereoselective synthesis of cyclopropyl alcohols using aryl aldehydes

Kim

Walsh

2012

J of Physical Organic Chem

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The prevalence of cyclopropanes in biologically active compounds has fueled many investigations into their preparation. Despite significant advances, more efficient methods for their catalytic enantioselective synthesis remain in demand. Previously, we reported a novel tandem approach to diastereo‐ and enantioenriched cyclopropyl alcohols. Our method involved an initial asymmetric C–C bond formation by addition of organozinc reagents to aldehydes catalyzed by a (−)‐MIB‐based catalyst. The resulting allylic zinc alkoxides were then subject to directed cyclopropanations. Although this approach provided cyclopropyl alcohols with very high enantio‐ and diastereoselectivity, it was successful with only aliphatic aldehydes. Aryl aldehyde substrates, on the other hand, exhibited low conversion and variable diastereomeric ratios. The present study is aimed at raising the stereoselectivity and yield of the aforementioned tandem reaction with aryl aldehyde substrates to make the method synthetically useful. Herein, we report the successful optimization of aryl aldehyde substrates in our one‐pot tandem approach leading to cyclopropyl alcohols with high yields and enantio‐ and diastereoselectivities. Copyright © 2012 John Wiley & Sons, Ltd.

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New Family of Cyclopropanating Reagents: Synthesis, Reactivity, and Stability Studies of Iodomethylzinc Phenoxides

Abstract: A valuable alternative to the traditional Simmons–Smith reagents is offered by the title compounds, as a result of their ease of preparation and high reactivities towards unfunctionalized olefins (see scheme).

Cited by 79 publications

References 24 publications

Synthesis of Spiro[2.2]pentanes and Spiro[2.3]hexanes Employing the Me₃Al/CH₂I₂ Reagent

Synthesis of Spiro[2.2]pentanes and Spiro[2.3]hexanes Employing the Me₃Al/CH₂I₂ Reagent

Cyclopropane Pipecolic Acids as Templates for Linear and Cyclic Peptidomimetics: Application in the Synthesis of an Arg‐Gly‐Asp (RGD)‐Containing Peptide as an α_vβ₃ Integrin Ligand

Tandem catalytic enantio‐ and diastereoselective synthesis of cyclopropyl alcohols using aryl aldehydes

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New Family of Cyclopropanating Reagents: Synthesis, Reactivity, and Stability Studies of Iodomethylzinc Phenoxides

Abstract: A valuable alternative to the traditional Simmons–Smith reagents is offered by the title compounds, as a result of their ease of preparation and high reactivities towards unfunctionalized olefins (see scheme).

Cited by 79 publications

References 24 publications

Synthesis of Spiro[2.2]pentanes and Spiro[2.3]hexanes Employing the Me3Al/CH2I2 Reagent

Synthesis of Spiro[2.2]pentanes and Spiro[2.3]hexanes Employing the Me3Al/CH2I2 Reagent

Cyclopropane Pipecolic Acids as Templates for Linear and Cyclic Peptidomimetics: Application in the Synthesis of an Arg‐Gly‐Asp (RGD)‐Containing Peptide as an αvβ3 Integrin Ligand

Tandem catalytic enantio‐ and diastereoselective synthesis of cyclopropyl alcohols using aryl aldehydes

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Synthesis of Spiro[2.2]pentanes and Spiro[2.3]hexanes Employing the Me₃Al/CH₂I₂ Reagent

Synthesis of Spiro[2.2]pentanes and Spiro[2.3]hexanes Employing the Me₃Al/CH₂I₂ Reagent

Cyclopropane Pipecolic Acids as Templates for Linear and Cyclic Peptidomimetics: Application in the Synthesis of an Arg‐Gly‐Asp (RGD)‐Containing Peptide as an α_vβ₃ Integrin Ligand