Cyclopropanation of Terminal Alkenes via Sequential Atom Transfer Radical Addition – 1,3-Elimination

An operationally simple protocol to affect an atom transfer radical addition (ATRA) of commercially available ICH<sub>2</sub>Bpin to terminal alkenes has been developed. The intermediate iodide can be transformed in a one-pot process into the corresponding cyclopropane upon treatment with tetrabutylammonium fluoride (TBAF). This method is highly selective for the cyclopropanation of unactivated terminal alkenes over non-terminal alkenes and electron deficient alkenes. Due to the mildness of the procedure, a wide range of functional groups such as esters, amides, alcohols, ketones, and vinylic cyclopropanes are well tolerated. The whole reaction sequence relies on simple reagents such dilauroyl peroxide (DLP) and TBAF and can be run on multi-gram scales in ethyl acetate as a solvent.

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Cyclopropanation of Terminal Alkenes via Sequential Atom Transfer Radical Addition – 1,3-Elimination

10.26434/chemrxiv.8325251 ◽

2019 ◽

Author(s):

Nicholas D. C. Tappin ◽

Weronika Michalska ◽

Simon Rohrbach ◽

Philippe Renaud

Keyword(s):

Ethyl Acetate ◽

Radical Addition ◽

Atom Transfer ◽

Reaction Sequence ◽

One Pot ◽

Tetrabutylammonium Fluoride ◽

Wide Range ◽

Atom Transfer Radical Addition ◽

Simple Protocol ◽

Terminal Alkenes

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Cyclopropanation of Terminal Alkenes through Sequential Atom‐Transfer Radical Addition/1,3‐Elimination

Angewandte Chemie International Edition ◽

10.1002/anie.201907962 ◽

2019 ◽

Vol 58 (40) ◽

pp. 14240-14244 ◽

Cited By ~ 8

Author(s):

Nicholas D. C. Tappin ◽

Weronika Michalska ◽

Simon Rohrbach ◽

Philippe Renaud

Keyword(s):

Radical Addition ◽

Atom Transfer ◽

Atom Transfer Radical Addition ◽

Terminal Alkenes

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Photoorganocatalytic Atom Transfer Radical Addition of Bromoacetonitrile to Aliphatic Olefins

Synthesis ◽

10.1055/s-0037-1610138 ◽

2018 ◽

Vol 50 (17) ◽

pp. 3395-3401 ◽

Cited By ~ 2

Author(s):

Christoforos Kokotos ◽

Errika Voutyritsa ◽

Nikolaos Nikitas ◽

Mary Apostolopoulou ◽

Anna Gerogiannopoulou

Keyword(s):

Radical Addition ◽

Synthetic Method ◽

Atom Transfer ◽

Wide Range ◽

Atom Transfer Radical Addition

A green and cheap protocol for the photocatalytic atom transfer radical addition (ATRA) of bromoacetonitrile to aliphatic alkenes is presented. The use of benzoin methyl ehter as the photocatalyst and irradiation using a household lightbulb leads to a highly useful synthetic method for the conversion of a wide range of substituted aliphatic olefins into the corresponding bromonitriles.

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Synthesis of Functionalized Polytriazoles via One-Pot Sequential Copper-Catalyzed Azide-Alkyne [3+2] Cycloaddition and Atom Transfer Radical Addition (ATRA)

Israel Journal of Chemistry ◽

10.1002/ijch.201100111 ◽

2012 ◽

Vol 52 (3-4) ◽

pp. 320-327 ◽

Cited By ~ 8

Author(s):

Carolynne L. Ricardo ◽

Tomislav Pintauer

Keyword(s):

Radical Addition ◽

Atom Transfer ◽

One Pot ◽

Atom Transfer Radical Addition

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One-Pot Sequential Azide-Alkyne [3+2] Cycloaddition and Atom Transfer Radical Addition (ATRA): Expanding the Scope of In Situ Copper(I) Regeneration in the Presence of Environmentally Benign Reducing Agent

European Journal of Inorganic Chemistry ◽

10.1002/ejic.201001335 ◽

2011 ◽

Vol 2011 (8) ◽

pp. 1292-1301 ◽

Cited By ~ 14

Author(s):

Carolynne L. Ricardo ◽

Tomislav Pintauer

Keyword(s):

Radical Addition ◽

Reducing Agent ◽

Environmentally Benign ◽

Atom Transfer ◽

One Pot ◽

Atom Transfer Radical Addition

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Ni–Catalyzed Difunctionalization of Alkynyl Bromides with Thiosulfonates and N-Arylthio Succinimides: A Convenient Synthesis of 1,2-Thiosulfonylethenes and 1,1-Dithioethenes

Synthesis ◽

10.1055/a-1482-2486 ◽

2021 ◽

Author(s):

Raju Jannapu Reddy ◽

Haritha Kumari Arram ◽

Jagadesh Kumar Jangam ◽

Rama Krishna Gamidi

Keyword(s):

Scale Up ◽

Radical Addition ◽

Cesium Carbonate ◽

One Pot ◽

Convenient Synthesis ◽

Wide Range ◽

Atom Transfer Radical Addition ◽

Plausible Mechanism ◽

High Yields ◽

And Control

An efficient Ni-catalyzed vicinal thiosulfonylation of 1-bromoalkynes with thiosulfonates in the presence of cesium carbonate has been described. An operationally simple and highly regioselective atom transfer radical addition (ATRA) of alkynyl bromides provided a wide range of (E)-1,2-thiosulfonylethenes (alpha-aryl-beta-thioarylvinyl sulfones) in moderate to high yields. The immense substrate scope of both alkynyl bromides and thiosulfonates were explored with a broad range of functional groups. Also, the indole derived 1,1-bromoalkenes were also successfully sightseen in 1,2-thiosulfonylation process. Moreover, the Ni-catalyzed geminal-dithiolation of alkynyl bromides with N-arylthio succinimides, thus providing 1,1-dithioalkenes in high yields. The present protocol is reliable at gram-scale, and a sequential one-pot bromination and thiosulfonylation of phenylacetylene have also been achieved in scale-up synthesis. A plausible mechanism is proposed to rationalize the experimental outcome and control experiments for the vicinal thiosulfonylation.

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