Mechanism‐Driven Elaboration of an Enantioselective Bromocyclopropanation Reaction of Allylic Alcohols

Taillemaud, Sylvain; Diercxsens, Nicolas; Gagnon, Alexandre; Charette, André B.

doi:10.1002/ange.201506083

Cited by 9 publications

(1 citation statement)

References 38 publications

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“…[24,25] The cyclopropane core is a crucial moiety for the pharmaceutical industry since it is one of the most often employed carbocycles for the creation of new drugs. [26] Due to distinct bonding characteristics, rigid skeleton, and extensive uses in various chemical processes, the cyclopropanes continue to be of paramount interest. Nevertheless, the preparation of substituted cyclopropanes remains challenging.…”

Section: Introductionmentioning

confidence: 99%

Cyclopropanation of Alkenes with Halodiazirines as Halocarbene Precursors in Continuous Flow

To,

Ollevier

2024

Chemistry A European J

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The cyclopropanation reaction of alkenes with photolytically‐generated chlorocarbenes from chlorodiazirines is reported as an effective way to prepare substituted 3‐chloro‐3‐aryl‐cyclopropanes. This practical and efficient approach allows the synthesis of various 3‐chloro‐3‐aryl‐cyclopropanes (32 examples) in continuous flow in 5‐minute residence time under light‐emitting diode (LED) irradiation. The conditions using 380 nm LED irradiation were successfully extended to the synthesis of substituted 3‐bromo‐3‐aryl‐cyclopropanes (3 examples).

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Section: Introductionmentioning

confidence: 99%

Cyclopropanation of Alkenes with Halodiazirines as Halocarbene Precursors in Continuous Flow

To,

Ollevier

2024

Chemistry A European J

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Alkali Metal Carbenoids: A Case of Higher Stability of the Heavier Congeners

Molitor

Gessner

2016

Angewandte Chemie

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As ar esult of the increased polarity of the metalcarbon bond when going down the group of the periodic table, the heavier alkali metal organyl compounds are generally more reactive and less stable than their lithium congeners.W en ow report ar everse trend for alkali metal carbenoids.S imple substitution of lithium by the heavier metals (Na, K) results in as ignificant stabilization of these usually highly reactive compounds.T his allows their isolation and handling at room temperature and the first structure elucidation of sodium and potassium carbenoids.T he control of stability was used to control reactivity and selectivity.H ence,t he Na and K carbenoids act as selective carbene-transfer reagents,w hereas the more labile lithium systems give rise to product mixtures. Additional fine tuning of the M À Ci nteraction by means of crownether addition further allows for control of the stability and reactivity.

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General Cyclopropane Assembly by Enantioselective Transfer of a Redox‐Active Carbene to Aliphatic Olefins

et al. 2019

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Asymmetric cyclopropane synthesis currently requires bespoke strategies, methods, substrates, and reagents, even when targeting similar compounds. This approach slows down discovery and limits available chemical space. Introduced herein is a practical and versatile diazocompound and its performance in the first unified asymmetric synthesis of functionalized cyclopropanes. The redox‐active leaving group in this reagent enhances the reactivity and selectivity of geminal carbene transfer. This effect allowed the asymmetric cyclopropanation of various olefins, including unfunctionalized aliphatic alkenes, that enables the three‐step total synthesis of (−)‐dictyopterene A. This unified synthetic approach delivers high enantioselectivities that are independent of the stereoelectronic properties of the functional groups transferred. Our results demonstrate that orthogonally differentiated diazocompounds are viable and advantageous equivalents of single‐carbon chirons.

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Mechanism‐Driven Elaboration of an Enantioselective Bromocyclopropanation Reaction of Allylic Alcohols

Cited by 9 publications

References 38 publications

Cyclopropanation of Alkenes with Halodiazirines as Halocarbene Precursors in Continuous Flow

Cyclopropanation of Alkenes with Halodiazirines as Halocarbene Precursors in Continuous Flow

Alkali Metal Carbenoids: A Case of Higher Stability of the Heavier Congeners

General Cyclopropane Assembly by Enantioselective Transfer of a Redox‐Active Carbene to Aliphatic Olefins

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