Formal asymmetric hydrobromination of styrenes via copper-catalyzed 1,3-halogen migration

Hoveln, Ryan Van; Schmid, Steven M.; Tretbar, Maik; Buttke, C. T.; Schomaker, Jennifer M.

doi:10.1039/c4sc02040e

Cited by 30 publications

(21 citation statements)

References 50 publications

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“…12 Fortunately, we have recently developed an asymmetric version of the 1,3-halogen migration reaction, which permitted a nonlinear effects study to gain insight into the nuclearity of the catalyst (Figure 1). 3 The absence of nonlinear effects support the assumption that the active catalyst in solution is monomeric in nature and argues against the presence of off-cycle organocopper dimers or higher order aggregates. 13,14 …”

Section: Resultsmentioning

confidence: 88%

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Mechanistic Studies of Copper(I)-Catalyzed 1,3-Halogen Migration

et al. 2015

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An ongoing challenge in modern catalysis is to identify and understand new modes of reactivity promoted by earth-abundant and inexpensive first-row transition metals. Herein, we report a mechanistic study of an unusual copper(I)-catalyzed 1,3-migration of 2-bromostyrenes that reincorporates the bromine activating group into the final product with concomitant borylation of the aryl halide bond. A combination of experimental and computational studies indicated this reaction does not involve any oxidation state changes at copper; rather, migration occurs through a series of formal sigmatropic shifts. Insight provided from these studies will be used to expand the utility of aryl copper species in synthesis and develop new ligands for enantioselective copper-catalyzed halogenation.

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Section: Resultsmentioning

confidence: 88%

“…7 While great strides have been made by several groups to promote Pd-like mechanistic pathways with first-row metals, 8,9 our group is taking an alternative approach by developing Cu-catalyzed reactions that invoke unusual mechanistic pathways involving no oxidation state changes at the metal center. 2,3 …”

Section: Introductionmentioning

confidence: 99%

Mechanistic Studies of Copper(I)-Catalyzed 1,3-Halogen Migration

et al. 2015

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“…552 (S,S)-Ph-BPE was found to provide the highest levels of ee for this transformation, although yields were typically low to moderate.…”

Section: Cu- Ag- and Au-catalyzed Reactionsmentioning

confidence: 94%

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

2016

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The high utility of halogenated organic compounds has prompted the development of a vast number of transformations which install the carbon-halogen motif. Traditional routes to these building blocks have commonly involved multiple steps, harsh reaction conditions, and the use of stoichiometric and/or toxic reagents. In this regard, using transition metals to catalyze the synthesis of organohalides has become a mature field in itself, and applying these technologies has allowed for a decrease in the production of waste, higher levels of regio- and stereoselectivity, and the ability to produce enantioenriched target compounds. Furthermore, transition metals offer the distinct advantage of possessing a diverse spectrum of mechanistic possibilities which translate to the capability to apply new substrate classes and afford novel and difficult-to-access structures. This Review provides comprehensive coverage of modern transition metal-catalyzed syntheses of organohalides via a diverse array of mechanisms. Attention is given to the seminal stoichiometric organometallic studies which led to the corresponding catalytic processes being realized. By breaking this field down into the synthesis of aryl, vinyl, and alkyl halides, it becomes clear which methods have surfaced as most favored for each individual class. In general, a pronounced shift toward the use of C-H bonds as key functional groups, in addition to methods which proceed by catalytic, radical-based mechanisms has occurred. Although always evolving, this field appears to be heading in the direction of using starting materials with a significantly lower degree of prefunctionalization in addition to less expensive and abundant metal catalysts.

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“…The reaction likely proceeded through Markovnikov hydrocupration, in which CuH was generated by the reaction of the Cu I salt with a borane. Based on this principle, an enantioselective version has been realized . Using chiral diphosphine ( S , S )‐Ph‐BPE afforded a range of enantioenriched benzyl bromides (Scheme ).…”

Section: Cuh‐catalyzed Functionalizationsmentioning

confidence: 99%

“…Based on this principle, an enantioselective version has been realized. [35] Using chiral diphosphine (S,S)-Ph-BPE afforded ar ange of enantioenriched benzylb romides (Scheme 18). These benzyl bromides are useful starting materials for various products.…”

Section: Other Cuh-catalyzedreactionsmentioning

confidence: 99%

Enantioselective Cu‐Catalyzed Functionalizations of Unactivated Alkenes

Sorádová

Šebesta

2016

ChemCatChem

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Copper hydride or copper boranyl species have already been used in reactions with Michael acceptors. Recently, notable advances have been described and the methodology extended to unactivated alkenes as well. In situ generated copper hydride ligated with chiral ligands is able to catalyze enantioselective aminations of alkenes. Furthermore, transient organocopper species formed upon initial hydrocupration of the alkene can be intercepted by other electrophiles such as imines, organohalides, or boranes.

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Formal asymmetric hydrobromination of styrenes via copper-catalyzed 1,3-halogen migration

Cited by 30 publications

References 50 publications

Mechanistic Studies of Copper(I)-Catalyzed 1,3-Halogen Migration

Mechanistic Studies of Copper(I)-Catalyzed 1,3-Halogen Migration

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Enantioselective Cu‐Catalyzed Functionalizations of Unactivated Alkenes

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