Nickel Catalyzed Oligomerization of 1,3-Dienes and Related Reactions

Jolly, P. W.

doi:10.1016/b978-008046518-0.00118-5

Cited by 20 publications

(4 citation statements)

References 188 publications

(131 reference statements)

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“…While high (10–20 mol %) loadings of nickel precatalysts have been reported for intramolecular [4+4]-cycloadditions of tethered dienes (Scheme B), attempts to apply these conditions for intermolecular coupling of substituted dienes have been met with low activity and/or low chemo- and regioselectivity for the [4+4]-cycloadducts (Scheme C) . Likewise, α-diimine and related ligands used in combination with iron salts and in situ reductants for the cyclodimerization of butadiene have been evaluated for [4+4]- and [4+2]-coupling reactions with other substrates. , Promising results were obtained with isolated examples (Scheme C); however, selectivity for [4+4]-cycloaddition was variable and limited in scope.…”

Section: Introductionmentioning

confidence: 99%

Regio- and Diastereoselective Iron-Catalyzed [4+4]-Cycloaddition of 1,3-Dienes

et al. 2019

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A family of single-component iron precatalysts for the [4+4]-cyclodimerization and intermolecular cross-[4+4]-cycloaddition of monosubstituted 1,3-dienes is described. Cyclooctadiene products were obtained with high regioselectivity, and catalyst-controlled access to either cisor transdiastereomers was achieved using 4-substituted diene substrates. Reactions conducted either with single-component precatalysts or with iron dihalide complexes activated in situ proved compatible with common organic functional groups and were applied on multi-gram scale (up to >100 g). Catalytically relevant, S = 1 iron complexes bearing 2-iminopyridine ligands, (R PI)FeL 2 (R PI = [2-(2,6-R 2-C 6 H 3-N=CMe)-C 5 H 4 N] where R = i PR or Me, L 2 = bis-olefin) were characterized by single-crystal X-ray diffraction, mößbauer spectroscopy, magnetic measurements, and dft calculations. The structural and spectroscopic parameters are consistent with an electronic structure description comprised of a high spin iron(I) center (S fe = 3/2) engaged in antiferromagnetically coupling with a ligand radical anion (S PI = −1/2). Mechanistic studies conducted with these single-component precatalysts-including kinetic analyses, 12 C/ 13 C isotope effect measurements, and in situ mößbauer spectroscopy-support a mechanism involving oxidative cyclization of two dienes that determines regio-and diastereoselectivity. Topographic steric maps derived from crystallographic data provided insights into the basis for the catalystcontrol through stereoselective oxidative cyclization and subsequent, stereospecific allylisomerization and CC bond-forming reductive elimination.

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Section: Introductionmentioning

confidence: 99%

Regio- and Diastereoselective Iron-Catalyzed [4+4]-Cycloaddition of 1,3-Dienes

et al. 2019

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“…The catalytic cyclodimerization of 1,3-dienes to give different cyclodimer products is an intriguing reaction and represents one of the famous textbook examples of a homogeneous catalytic reaction . Several transition-metal complexes are known to actively catalyze the cyclodimerization reaction; however, nickel complexes represent the most versatile and useful catalytic systems …”

Section: Introductionmentioning

confidence: 99%

[Ni⁰L]-Catalyzed Cyclodimerization of 1,3-Butadiene: A Comprehensive Density Functional Investigation Based on the Generic [(C₄H₆)₂Ni⁰PH₃] Catalyst

Tobisch

Ziegler

2002

J. Am. Chem. Soc.

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We present a comprehensive theoretical investigation of the mechanism for cyclodimerization of butadiene by the generic [bis(butadiene)Ni(0)PH(3)] catalyst employing a gradient-corrected DFT method. We have explored all critical elementary steps of the whole catalytic cycle, namely, oxidative coupling of two butadienes, reductive elimination under ring closure, and allylic isomerization. Oxidative coupling of two butadienes in the [bis(butadiene)Ni(0)L] complex and reductive elimination in the [(bis(eta(3))-octadienediyl)Ni(II)L] species take place under different stereocontrol, which makes isomerization indispensable. Commencing from a preestablished equilibrium between several configurations of the [(octadienediyl)Ni(II)L] complex, the major cyclodimer products, namely, VCH, cis-1,2-DVCB, and cis,cis-COD, are formed along competing reaction paths via reductive elimination, which is found to be the overall rate-determining step. Careful exploration of different possible conceivable routes revealed that bis(eta(1)) species are not involved as critical intermediates either in reductive elimination or in isomerization along the most feasible pathway. The regulation of the selectivity of the cyclodimer formation based on both thermodynamic and kinetic considerations is outlined.

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“…The catalytic cyclodimerization of 1,3-dienes mediated by transition metal complexes is one of the key processes in homogeneous catalysis . Ligand-stabilized zerovalent nickel [Ni 0 L] complexes, in particular, have been shown as the most versatile and useful catalysts .…”

Section: Introductionmentioning

confidence: 99%

[Ni⁰L]-Catalyzed Cyclodimerization of 1,3-Butadiene: A Density Functional Investigation of the Influence of Electronic and Steric Factors on the Regulation of the Selectivity

Tobisch

Ziegler

2002

J. Am. Chem. Soc.

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We present a comprehensive theoretical investigation of the influence of the ligand L on the regulation of the product selectivity for the [Ni(0)L]-catalyzed cyclodimerization of 1,3-butadiene. The investigation was based on density functional theory (DFT) and a combined DFT and molecular mechanics (QM/MM) approach for the real [bis(butadiene)Ni(0)L] catalysts with L = PMe(3), I; PPh(3), II; P((i)Pr)(3), III; and P(OPh)(3), IV. The role of electronic and steric effects has been elucidated for all crucial elementary steps of the entire catalytic cycle. Allylic isomerization, allylic enantioface conversion, as well as oxidative coupling are shown to be influenced to a minor extent by electronic and steric effects. In contrast, the ligand's properties have a distinct influence on the preestablished equilibrium between the eta(3),eta(1)(C(1)) and bis-eta(3) forms 2 and 4, respectively, of the [(octadienediyl)Ni(II)L] complex and on the rate-determining reductive elimination following competing routes for generation of either VCH, cis-1,2-DVCB, or cis,cis-COD. Electronic factors are shown to predominantly determine the position of the kinetically mobile 2 right harpoon over left harpoon 4 equilibrium. 4 is the prevailing species for ligands L that are pi-acceptors (L = P(OPh)(3)) or weak sigma-donors (L = PPh(3)), while stronger sigma-donors (L = PMe(3), P((i)Pr)(3)) displace the equilibrium to the left. Steric bulk on the ligand as well as its pi-acceptor ability act to facilitate the reductive elimination, while sigma-donor abilities serve to retard this process. Electronic and steric factors are found to not influence uniformly the reductive elimination routes with either 2 or 4 involved. The regulation of the product selectivity is elucidated on the basis of both thermodynamic and kinetic considerations.

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Nickel Catalyzed Oligomerization of 1,3-Dienes and Related Reactions

Cited by 20 publications

References 188 publications

Regio- and Diastereoselective Iron-Catalyzed [4+4]-Cycloaddition of 1,3-Dienes

Regio- and Diastereoselective Iron-Catalyzed [4+4]-Cycloaddition of 1,3-Dienes

[Ni⁰L]-Catalyzed Cyclodimerization of 1,3-Butadiene: A Comprehensive Density Functional Investigation Based on the Generic [(C₄H₆)₂Ni⁰PH₃] Catalyst

[Ni⁰L]-Catalyzed Cyclodimerization of 1,3-Butadiene: A Density Functional Investigation of the Influence of Electronic and Steric Factors on the Regulation of the Selectivity

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Nickel Catalyzed Oligomerization of 1,3-Dienes and Related Reactions

Cited by 20 publications

References 188 publications

Regio- and Diastereoselective Iron-Catalyzed [4+4]-Cycloaddition of 1,3-Dienes

Regio- and Diastereoselective Iron-Catalyzed [4+4]-Cycloaddition of 1,3-Dienes

[Ni0L]-Catalyzed Cyclodimerization of 1,3-Butadiene: A Comprehensive Density Functional Investigation Based on the Generic [(C4H6)2Ni0PH3] Catalyst

[Ni0L]-Catalyzed Cyclodimerization of 1,3-Butadiene: A Density Functional Investigation of the Influence of Electronic and Steric Factors on the Regulation of the Selectivity

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[Ni⁰L]-Catalyzed Cyclodimerization of 1,3-Butadiene: A Comprehensive Density Functional Investigation Based on the Generic [(C₄H₆)₂Ni⁰PH₃] Catalyst

[Ni⁰L]-Catalyzed Cyclodimerization of 1,3-Butadiene: A Density Functional Investigation of the Influence of Electronic and Steric Factors on the Regulation of the Selectivity