Rhodium-Complex-Catalyzed Addition Reactions of Chloroacetyl Chlorides to Alkynes

Kashiwabara, Taigo; Fuse, Kouichiro; Hua, Ruimao; Tanaka, Masato

doi:10.1021/ol802260w

Cited by 71 publications

(14 citation statements)

References 19 publications

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“…This reaction was extended to the use of chloroacetyl chloride by the same authors in 2008 by using AsPh 3 as the ligand instead of PPh 3 (Scheme 189). 342 In 2009, Tanaka and co-workers reported the synthesis of 1,4-dichlorobutadienes by a Rh-catalyzed alkyne dimerization process ( Scheme 190). 343 This reaction is based on earlier work involving stoichiometric alkyne dimerization/halogenation using Zr/Ti complexes 344,345 or Pd-catalyzed iodinative alkyne dimerization, 346 and uses trichloroacetyl chlroride as the halide source.…”

Section: Carbohalogenation Of Alkynes By Halometalationmentioning

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: Carbohalogenation Of Alkynes By Halometalationmentioning

confidence: 99%

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

2016

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“…It is used as a protecting group (28) for alcohols and amines. The acid chloride part is used in many acylation reactions with alcohols, amines, (29)(30)(31)(32) alkynes (33) and also in Friedel-Crafts reactions (34,35). Similarly the α-chlorine can be replaced by many nucleophiles (OH ─ , NH 2 ─ , SH ─ etc.)…”

Section: Introductionmentioning

confidence: 99%

An expedient and rapid green chemical synthesis of N-chloroacetanilides and amides using acid chlorides under metal-free neutral conditions

Balaji

Dalal

2018

Green Chemistry Letters and Reviews

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We are reporting for the first time, rapid N-chloroacetylation of anilines and amines in phosphate buffer within 20 min. Primary and secondary amino derivatives (amines, anilines) were efficiently condensed with various acid chlorides (containing aliphatic, aromatic, cyclic and heteroaromatic units). We have also shown that the modification of the electrophilic nature of the substituents on the acid chloride did not affect the product formation and the required amides are formed in high yields. The major advantage of this process is highlighted by the ease of product isolation (simple filtration/precipitation). This process represents the first example of a metal-free, green chemical synthesis under neutral conditions to provide an eco-friendly, easily scalable and robust process for the preparation of amides that expands the scope, utility and applicability of acid chlorides.

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“…Tanaka and co-workers showed that such reactions proceed with the retention of CO in the presence of the same catalyst when chloroformate esters, which are particularly electron-poor substrates, are used. [8] Over the following years, the Tanaka research group developed tailored procedures for the stereoselective, CO-retentive addition of ethoxalyl chloride, [9] perfluorinated acid chlorides, [10] and chloroacetyl chlorides [11] (Scheme 2, bottom). For the rhodium-based catalyst systems, the degree of CO retention appears to depend solely on the acid chloride substrate.…”

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confidence: 99%

Stereoselective Synthesis of β‐Chlorovinyl Ketones and Arenes by the Catalytic Addition of Acid Chlorides to Alkynes

Gooßen¹,

Rodríguez²,

Gooßen³

2009

Angew Chem Int Ed

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New cats, new tricks: Complementary iridium catalysts enable the Z‐selective catalytic addition of acid chlorides to alkynes. Depending on the ligand, the reaction proceeds with or without decarbonylation to give β‐chlorovinyl‐substituted arenes or ketones: useful intermediates for the synthesis of heterocycles. cod=cyclooctadiene, IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene), RuPhos=2‐dicyclohexylphosphanyl‐2′,6′‐diisopropoxy‐1,1′‐biphenyl.

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Rhodium-Complex-Catalyzed Addition Reactions of Chloroacetyl Chlorides to Alkynes

Abstract: The addition reaction of chloroacetyl chloride derivatives with terminal alkynes was found to be catalyzed by Rh(acac)(CO)(AsPh(3)) to afford (Z)-1,4-dichloro-3-buten-2-one derivatives, which displayed diverse reactivities in synthetic elaboration.

Cited by 71 publications

References 19 publications

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

An expedient and rapid green chemical synthesis of N-chloroacetanilides and amides using acid chlorides under metal-free neutral conditions

Stereoselective Synthesis of β‐Chlorovinyl Ketones and Arenes by the Catalytic Addition of Acid Chlorides to Alkynes

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