Palladium-Catalyzed Carbohalogenation: Bromide to Iodide Exchange and Domino Processes

Newman, Stephen G.; Howell, Jennifer; Nicolaus, Norman; Lautens, Mark

doi:10.1021/ja206099t

Cited by 187 publications

(69 citation statements)

References 34 publications

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“…449 The authors also reported the cyclization of polyunsaturated aryl iodides which provided access to complex polycyclic scaffolds with the retention of the reactive functionality. For example, fused lactam 445 could be obtained in 91% in 5:1 dr or 89% in 3:1 dr from the corresponding aryl iodide 443 or aryl bromide 444, respectively (Scheme 287).…”

Section: Synthesis Of Alkyl Halidesmentioning

confidence: 99%

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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Section: Synthesis Of Alkyl Halidesmentioning

confidence: 99%

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

2016

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“…As discussed earlier, the palladium-catalyzed couplings of alkenyl halides with alkenes can give rise to the formation of π-allylpalladium complexes, which can then be attacked by internal nucleophiles including hydroxy groups to yield various oxacyclic systems (Scheme 8.38) [343]. Lautens et al [344] reported the termination of a cascade of two intramolecular Heck 5-exo-trig carbopalladations by iodide leading from the o-bromobenzamide derivative 159 in the presence of potassium iodide to the heterotricycle 160 in 88% yield (Scheme 8.39). The same transformation was observed for the o-iodo analog of 159 and other o-iodophenyl derivatives with alkenyl side chains leading to various benzannelated dihydrofuran and dihydropyrrole derivatives.…”

Section: Palladium-catalyzed Reactions Involving Nucleophilic Substratesmentioning

confidence: 99%

“…Scheme 8.39Termination of a two-step 5-exo-trig carbopalladation cascade by reductive elimination from an alkylpalladium iodide intermediate[344].…”

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Cross‐Coupling of Organyl Halides with Alkenes – The Heck Reaction

Bräse¹,

Meijere²

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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The carbopalladation of an alkene by an organylpalladium halide is the essential step in one of the major contemporary metal-catalyzed C-C coupling reactions. About 45 years ago, a Japanese and an American group almost simultaneously designed and executed palladium-mediated coupling reactions of aryl and alkenyl halides with alkenes [1]. In subsequent investigations, Richard Heck and his group developed this reaction into a catalytic transformation and started to demonstrate its usefulness as well as its rather broad scope. The real push to utilize this powerful C-C-bondforming process, however, started only around the mid-1980s, and by now, an impressive number of publications have established the meanwhile so-called Heck reaction [2] 1) as an indispensable method in Organic Synthesis [3][4][5][6][7]. The universal recognition of the importance of the Heck reaction and the Negishi as well as the Suzuki coupling eventually won the Nobel Prize for Richard Heck along with Ei-ichi Negishi and Akira Suzuki in 2010. The applications of the Heck reaction range from the preparation of -functionalized and unfunctionalized -hydrocarbons, novel polymers, and dyes to new advanced enantioselective syntheses of natural products and biologically active nonnatural compounds. The more or less simultaneous developments of mechanistically related variants, namely, the Kumada, Suzuki, Stille, Hiyama, and Negishi coupling reactions (Chapters 12, 2, 3, 4, and 15, respectively) of metallated alkenes and arenes with aryl and alkenyl halides or the metal-catalyzed formation and cycloisomerization of enynes have drawn profit from the improvement of and mechanistic insights into the Heck reaction. This, of course, applies vice versa as well. Using only a catalytic amount of a palladium(0) complex or a precursor to a palladium species, the Heck reaction can bring about unprecedented structural changes, particularly when conducted intramolecularly. The full potential of this palladium-catalyzed process is still being further explored as demonstrated by a total of over 7000 publications in the past 40 years by 1) The alkynylation of aryl and alkenyl halides, frequently also considered as Heck reactions, is described in Chapter 6.

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“…[10] However, no useful quantity of carbobromination product was obtained under the previous standard conditions. The reaction afforded a 95 % yield of iodide 3 when two equivalents of KI were added (Scheme 5).…”

Section: Sp 3 -Carbon-halogen Bond Formationmentioning

confidence: 99%

Carbon–Halogen Bond Formation by the Reductive Elimination of Pd^II Species

Jiang

Liu

2012

Asian J Org Chem

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It is well known that Pd 0 undergoes oxidative addition to organic halides, especially aryl or vinyl halides. In the contrast, the formation of organic halides by reductive elimination of RPd II X (X= halogen) has been mostly ignored until very recently. This Focus Review discusses recent developments in palladium-catalyzed carbon-halogen bond formation by the reductive elimination of RPd II X. These new developments have enriched the scope of palladium-catalyzed reactions, and provide a new way to construct carbon-halogen bonds.

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Palladium-Catalyzed Carbohalogenation: Bromide to Iodide Exchange and Domino Processes

Cited by 187 publications

References 34 publications

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Cross‐Coupling of Organyl Halides with Alkenes – The Heck Reaction

Carbon–Halogen Bond Formation by the Reductive Elimination of Pd^II Species

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Palladium-Catalyzed Carbohalogenation: Bromide to Iodide Exchange and Domino Processes

Cited by 187 publications

References 34 publications

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Cross‐Coupling of Organyl Halides with Alkenes – The Heck Reaction

Carbon–Halogen Bond Formation by the Reductive Elimination of PdII Species

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Carbon–Halogen Bond Formation by the Reductive Elimination of Pd^II Species