Mechanisms of oxidative addition of organic halides to Group 8 transition-metal complexes

Stille, J. K.; Lau, Kreisler S.Y.

doi:10.1021/ar50120a002

Cited by 364 publications

(180 citation statements)

References 60 publications

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“…mostly, more crowded systems [1][2][3]. It also agrees with the stereochemistry of the reverse proc ess, carbonyl insertion reactions [5][6][7]. This provides further support for the notion [10] that biological carbonyl insertion reactions, even in sterically unhin dered cases like the formation of an acetyl group by "carbonyl insertion" into a metal-methyl bond, also proceed with retention of configuration.…”

Section: Discussionsupporting

confidence: 74%

Steric Course of the Rhodium-Catalyzed Decarbonylation of Chiral 4-M ethyl-[1-³H,2-²H₁]pentanal

Otsuka

Floss

1987

Zeitschrift Für Naturforschung C

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Dedicated to Professor Helmut Simon on the occasion o f his 60th birthdayStereochemistry, Decarbonylation, Rhodium Catalyst, Chiral Methyl Group, 4-Methylpentanal (R)-and (5)-4-methyl-[l-3H,2-2H!]pentanal were prepared from l -and D-leucine via leucic acid and (S)-and (ft)-4-methyl-[2-2H,]pentanoic acid. Decarbonylation of these samples with tris-(triphenylphosphine)rhodium chloride followed by Kuhn-Roth oxidation of the resulting 2-methylbutane gave chiral acetic acid of 35% e.e. S and 31% e.e. R configuration, respectively. The decarbonylation reaction thus proceeds with net retention of configuration, possibly accom panied by some racemization.The stereochemistry of the decarbonylation of aldehydes catalyzed by tris-(triphenylphosphine)rhodium chloride has been examined in a few cases [1]. The reaction was found to proceed with high stereoselectivity, except when the a-carbon car ried an electron-donating group like -OCH3, and net retention of configuration. However, all the cases studied involved hindered aldehydes in which the formyl group was attached to a quaternary car bon. In the analogous decarbonylation of acid chlorides [2, 3] net retention of configuration was also observed, but these reactions were accompanied by a high degree of racemization. However, the cases studied here also involved less crowded systems in which the carbonyl group was attached to a primary or secondary carbon. These reactions represent the reversal of the so-called carbonyl insertions into transition metal-carbon bonds [4], which, mechanis tically, are actually migrations of a metal-bound alkyl group to an adjacent bound carbon monoxide. These, in the cases studied, also proceed with reten tion of configuration of the alkyl group [5, cf. 4, 6, 7].In the course of studies on stereochemical aspects of the biosynthesis of ergot alkaloids [8] we were faced with the problem of determining the configura tion of 4-methylpentanoic acid stereospecifically monodeuterated at C-2 on ^g samples obtained in an impure state from complex reaction mixtures. It oc curred to us that the limitation of quantity could be overcome by converting the acid to the 1-tritiated alcohol by reduction with tritiated LiBH4, followed by oxidation to the aldehyde and decarbonylation to give 2-methylbutane carrying a chiral methyl group at C-4 (Scheme I). In this sequence the tritiated, deuterated alcohol could be diluted with ample car rier material, allowing the subsequent chemical steps to be carried out on a more manageable scale.To explore the feasibility of this degradation se quence it was necessary to determine whether the decarbonylation of an uncrowded aldehyde like 4-methylpentanal also proceeds stereospecifically with retention of configuration. The results are reported here because of the current interest in an important biochemical carbonyl insertion reaction, the synthe sis of acetic acid in anaerobic organisms [9], and its stereochemistry [10]. ResultsTo examine the steric course of the transition metal-catalyzed decarbonylation of 4-methylpenta...

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Section: Discussionsupporting

confidence: 74%

Steric Course of the Rhodium-Catalyzed Decarbonylation of Chiral 4-M ethyl-[1-³H,2-²H₁]pentanal

Otsuka

Floss

1987

Zeitschrift Für Naturforschung C

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“…The ligands DPPQ [11], Me-DPPQ [12], TtBQ and TMQ [5], MeTtBQ [13], Me-TMQ [10], and of the complexes 1, 4 [8] and 2,3 http://dx.doi.org/10.1016/j.poly.2015.07.049 0277-5387/Ó 2015 Elsevier Ltd. All rights reserved. [5] were obtained according to published protocols, whereas the complexes 5 and 6 are newly synthesized compounds.…”

Section: General Considerationsmentioning

confidence: 99%

“…Addition of a stoichiometric amount of the ligands Me-TtBQ or Me-TMQ to a solution of the complex Pd 2 (DBA) 3 . CHCl 3 in acetone in the presence of a slight excess of dmfu (3:1) under inert atmosphere (Ar) yields the complexes 5 and 6 as stable pale-yellow and yellow precipitates, respectively.…”

Section: General Considerationsmentioning

confidence: 99%

“…In particular, the Pd(0) derivatives are often employed in oxidative addition involving organic halides which represents the first step of important cross coupling processes [2]. The reactivity of the organic halides toward Pd(0) complexes was widely studied as a function of their nature and structure [1a] but their influence on the intimate mechanism is still a matter of discussion [3,4]. In this respect, we have recently published a paper in which we discussed some aspects of the preferential formation of allenyl or propargyl tautomeric derivatives when propargyl halides react with some dimethylfumarate (dmfu) stabilized Pd(0) complexes bearing thioetheric or diphenyl phosphine quinoline-based ancillary ligands.…”

Section: Introductionmentioning

confidence: 99%

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Oxidative addition of organic halides on palladium(0) complexes stabilized by dimethylfumarate and quinoline-based N–P or N–S spectator ligands

et al. 2015

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a b s t r a c tWe have studied the oxidative addition of some organic halides on palladium(0) dimethylfumarate complexes bearing heteroditopic (N-P or N-S) quinoline-based spectator ligands from the experimental and theoretical point of view. We have measured the half-life of some oxidative addition reactions carried out in two different solvents (CD 2 Cl 2 and CD 3 CN). The reactions were studied under mild conditions by NMR and the reactivities of different oxidants towards the complexes under study were compared. The rates of reaction were influenced by the nature of the spectator ligands and the solvent. The thioquinoline derivatives display a higher reactivity than that of the phosphoquinoline complexes and in general the reaction rates are higher in CD 3 CN than in CD 2 Cl 2 , although such a behavior is not always observed. We propose a plausible mechanism for the oxidative reaction in different solvents based on the experimental results and an adequate computational approach. Finally, the solid state structures of two reaction products were resolved and reported.

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“…20,55.39,114.16,124.82,126.24,126.89,127.97,128.02,128.34,128.35,129.22,129.48,130.77,133.06,136.27,141.24,151.42,153.19,158.02;IR (CHCIa) Hz, 1H), 9.34 (s, 1H); 13 C NMR (CDCI3) S 14.34,62.43,82.66,90.04,109.27,125.52,126.54,128.28,128.33,128.44,129.43,130.05,132.37,137.40,139.21,153.75,154.04,157.31;IR (CHCI3) …”

Section: -Benzyl-3-phenylisoquinoline (41)mentioning

confidence: 99%

New palladium-catalyzed approaches to heterocycles and carbocycles

Dai

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Mechanisms of oxidative addition of organic halides to Group 8 transition-metal complexes

Cited by 364 publications

References 60 publications

Steric Course of the Rhodium-Catalyzed Decarbonylation of Chiral 4-M ethyl-[1-³H,2-²H₁]pentanal

Steric Course of the Rhodium-Catalyzed Decarbonylation of Chiral 4-M ethyl-[1-³H,2-²H₁]pentanal

Oxidative addition of organic halides on palladium(0) complexes stabilized by dimethylfumarate and quinoline-based N–P or N–S spectator ligands

New palladium-catalyzed approaches to heterocycles and carbocycles

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Mechanisms of oxidative addition of organic halides to Group 8 transition-metal complexes

Cited by 364 publications

References 60 publications

Steric Course of the Rhodium-Catalyzed Decarbonylation of Chiral 4-M ethyl-[1-3H,2-2H1]pentanal

Steric Course of the Rhodium-Catalyzed Decarbonylation of Chiral 4-M ethyl-[1-3H,2-2H1]pentanal

Oxidative addition of organic halides on palladium(0) complexes stabilized by dimethylfumarate and quinoline-based N–P or N–S spectator ligands

New palladium-catalyzed approaches to heterocycles and carbocycles

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Steric Course of the Rhodium-Catalyzed Decarbonylation of Chiral 4-M ethyl-[1-³H,2-²H₁]pentanal

Steric Course of the Rhodium-Catalyzed Decarbonylation of Chiral 4-M ethyl-[1-³H,2-²H₁]pentanal