Synthesis of 1,4-Dichloro-1,3-butadienes by Rhodium Complex Catalyzed Reaction of Terminal Alkynes with Trichloroacetyl Chloride

Kashiwabara, Taigo; Fuse, Kouichirou; Muramatsu, Takeshi; Tanaka, Masato

doi:10.1021/jo902088p

Cited by 12 publications

(3 citation statements)

References 51 publications

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“…mer,trans -RhCl 3 (CO)(PMe 3 ) 2 ( mer,trans -10 ), which was detected before the replacement of the solvent from toluene- d 8 to CDCl 3 , was not found either, but instead, fac , cis -RhCl 3 (CO)(PMe 3 ) 2 ( fac,cis -10 ) was found in the CDCl 3 solution. In view of facile isomerization between mer,trans -10 and fac,cis -10 , depending on the polarity of the solvent, mer,trans -10 found in the thermolysis mixture ( a toluene-d 8 solution ) appeared to have isomerized to fac,cis -10 when the toluene- d 8 solvent was replaced by CDCl 3 .…”

Section: Resultsmentioning

confidence: 99%

Arylglyoxylrhodium Complexes, Their Thermolysis, and Attempted Generation by Carbonylation of an Aroylrhodium Complex

Kashiwabara

Tanaka

2010

Organometallics

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Reactions of ArCOCOCl (Ar = p-ClC6H4, Ph) with Rh(acac)(CO)2 proceeded readily to afford dimeric arylglyoxyl rhodium complexes [Rh(μ-Cl)(acac)(CO)(COCOAr)]2. [Rh(μ-Cl)(acac)(CO){COCO(p-ClC6H4)}]2 was characterized by X-ray diffraction. Thermolysis of the products showed that [Rh(μ-Cl)(acac)(CO){COCO(p-ClC6H4)}]2 was more stable than [Rh(μ-Cl)(acac)(CO)(COCOPh)]2. The reaction of p-CH3OC6H4COCOCl with Rh(acac)(CO)2 did not form a similar dimeric complex as final product, but gave p-CH3OC6H4COCl as major product, showing thermal instability of corresponding arylglyoxyl and aroyl rhodium complexes. The reaction of C6F5COCOCl did not form a simlar dimeric complex either, but a mononuclear complex RhCl(acac)(COCOC6F5)(CO)2 was generated as a transient intermediate, which was readily transformed to a furanone arising from reductive elimination of the acac ligand and C6F5COCO moiety followed by cyclization. In the thermolysis of [Rh(μ-Cl)(acac)(CO)(COCOAr)]2, only ArCOCl and Rh(acac)(CO)2 were formed, and any ArCORh species could not be detected during the thermolysis process. However, the reaction of Rh(acac)(CO)2 with PhCOCl formed RhCl(acac)(CO)2(COPh), albeit only to a small extent, suggesting that the reaction is not thermodynamically favored. The reaction of RhCl(CO)(PMe3)2 with p-ClC6H4COCOCl also proceeded cleanly to furnish p-ClC6H4COCORhCl2(CO)(PMe3)2. Thermolysis of the complex formed p-ClC6H4CORhCl2(CO)(PMe3)2, indicating slow reductive elimination of ClC6H4COCl as compared with the ArCORh species, generated in the thermolysis of [Rh(μ-Cl)(acac)(CO)(COCOAr)]2. Treatment of ClC6H4CORhCl2(CO)(PMe3)2 with carbon monoxide generates p-ClC6H4COCORhCl2(CO)(PMe3)2, although the yield was low.

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Section: Resultsmentioning

confidence: 99%

Arylglyoxylrhodium Complexes, Their Thermolysis, and Attempted Generation by Carbonylation of an Aroylrhodium Complex

Kashiwabara

Tanaka

2010

Organometallics

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“…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. The authors noted that more bulky ligands were best in this chemistry and that PhCl was the optimal solvent.…”

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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“…The rhodium-phosphorus coupling constant is in a typical range for a binuclear Rh(III) spezies. [124][125][126][127] The 19 F NMR spectrum depicts three resonances at δ = −65.5 (CF 3 ), −66.5 (F α ) and −143.6 (F β ) ppm in a 6 : 2 : 2 ratio for the propenyl ligand. The chemical shifts are in a similar range than those found for 12 or 13.…”

Section: Dalton Transactions Papermentioning

confidence: 99%

Synthesis of a rhodium(i) germyl complex: a useful tool for C–H and C–F bond activation reactions

Ahrens

Braun

et al. 2016

Dalton Trans.

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The dihydrido germyl complex cis,fac-[Rh(GePh3)(H)2(PEt3)3] (2) was synthesized by an oxidative addition of HGePh3 at [Rh(H)(PEt3)3] (1). Treatment of 2 with neohexene generated the rhodium(i) germyl complex [Rh(GePh3)(PEt3)3] (3). Alternatively, treatment of the methyl complex [Rh(CH3)(PEt3)3] (4) with HGePh3 furnished at room temperature also 3. Low-temperature NMR measurements revealed an initial formation of the oxidative addition product fac-[Rh(GePh3)(H)(CH3)(PEt3)3] (5), which transforms into the intermediate complex [Rh(GePh3)(H)(CH3)(PEt3)2] (6) by dissociation of a triethylphosphine ligand. The reductive elimination of methane and coordination of PEt3 afforded the germyl complex 3. Treatment of 3 with CO gave the biscarbonyl complex [Rh(GePh3)(CO)2(PEt3)2] (7). The molecular structures of the complexes 2, 3 and 7 were determined by X-ray crystallography. The germyl complex 3 reacted with 2,3,5,6-tetrafluoropyridine or pentafluorobenzene to furnish the C-H activation products [Rh(4-C5NF4)(PEt3)3] (8) and [Rh(C6F5)(PEt3)3] (9), respectively. The reaction of 3 with hexafluorobenzene or perfluorotoluene gave selectively the C-F activation products 9 and [Rh(4-C6F4CF3)(PEt3)3] (10). Treatment of 3 with pentafluoropyridine resulted in the formation of the C-F activation products 8 and [Rh(2-C5NF4)(PEt3)3] (11) in a 1 : 10 ratio. The two isomeric activation compounds [Rh{(E)-CF[double bond, length as m-dash]CF(CF3)}(PEt3)3] (12) and [Rh{(Z)-CF[double bond, length as m-dash]CF(CF3)}(PEt3)3] (13) were obtained in a 3 : 1 ratio by reaction of 3 with hexafluoropropene. On exposure to oxygen the highly air sensitive complex 12 reacts to yield the peroxido-bridged dirhodium complex [Rh{(E)-CF[double bond, length as m-dash]CF(CF3)}(μ-κ(1):η(2)-O2)(PEt3)2]2 (14). The molecular structure of 14 was determined by X-ray crystallography.

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Synthesis of 1,4-Dichloro-1,3-butadienes by Rhodium Complex Catalyzed Reaction of Terminal Alkynes with Trichloroacetyl Chloride

Cited by 12 publications

References 51 publications

Arylglyoxylrhodium Complexes, Their Thermolysis, and Attempted Generation by Carbonylation of an Aroylrhodium Complex

Arylglyoxylrhodium Complexes, Their Thermolysis, and Attempted Generation by Carbonylation of an Aroylrhodium Complex

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Synthesis of a rhodium(i) germyl complex: a useful tool for C–H and C–F bond activation reactions

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