Mechanism of thermal decomposition of n-butyl(tri-n-butylphosphine) copper(I)

Whitesides, George M.; Stedronsky, Erwin R.; Casey, Charles P.; Filippo, Joseph San

doi:10.1021/ja00708a067

Cited by 117 publications

(34 citation statements)

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“…Analogous reactivity has also been reported for [Cu n Pr] n and [Cu n Bu] n , 28 as well as phosphine-coordinated [(R 0 3 P) x CuR] (R = Et, n Pr, n Bu, or i Bu; R 0 3 P = PPh 3 , PCy 3 , or P n Bu 3 ) complexes. 18,20,29 The NMR studies outlined above are consistent with the following sequence of reactions for copper metal deposition from [Cu(PyrIm iPr ) 2 ] (6a) with ZnEt 2 (Scheme 5): (1) Reaction of 6a with ZnEt 2 to form "(PyrIm iPr )CuEt" and [(PyrIm iPr )ZnEt] (12a) or [Zn(PyrIm iPr ) 2 ] (12b). (2) Decomposition of "(PyrIm iPr )CuEt" by reaction with 6a to eliminate PyrIm iPr -Et (10b) (at low ZnEt 2 reaction stoichiometries) or bimolecular reductive elimination of n-butane (at higher (4) β-Hydride elimination of ethylene from [CuEt] n to form "CuH".…”

Section: Scheme 2 Independent Synthesis Of Complex 8 (8) a Copper(i)supporting

confidence: 58%

Solution Reactions of a Bis(pyrrolylaldiminate)copper(II) Complex with Peralkyl Zinc, Aluminum, and Boron Reagents: Investigation of the Pathways Responsible for Copper Metal Deposition

et al. 2010

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The solution reactions of bis(N-isopropylpyrrolylaldiminate)copper(II) (CuL 2 ) with AlMe 3 , BEt 3 , and ZnEt 2 have been studied. In all cases, reduction occurs in two stages via a stable copper(I) pyrrolylaldiminate complex (Cu 2 L 2 ), with each stage initiated by copper alkyl complex formation. Reduction from "LCuR" (R=Me or Et) occurs with release of R 2 or L-R, consistent with bimolecular C-C or C-N bond-forming reductive elimination. At room temperature or below, copper deposition from "CuMe" occurs exclusively via reductive elimination of ethane, whereas decomposition of "CuEt" yields ethylene, ethane, and hydrogen, indicative of both β-hydride elimination and reductive elimination. The reaction byproducts [Cu 2 L 2 ], [LAlMe 2 ], [L 2 AlMe], [AlL 3 ], [LBEt 2 ], [LZnEt], [ZnL 2 ], L-Me, and L-Et were synthesized independently and isolated as pure compounds. All compounds are thermally stable, with the exception of LZnEt, which undergoes ligand redistribution to form ZnL 2 and ZnEt 2 in solution and as a solid at elevated temperatures. With the exception of [LZnEt] and [Cu 2 L 2 ], these complexes are also volatile; monoligated [LAlMe 2 ] and [LBEt 2 ] are particularly volatile, and therefore more desirable as byproducts in ALD or pulsed-CVD.

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Section: Scheme 2 Independent Synthesis Of Complex 8 (8) a Copper(i)supporting

confidence: 58%

Solution Reactions of a Bis(pyrrolylaldiminate)copper(II) Complex with Peralkyl Zinc, Aluminum, and Boron Reagents: Investigation of the Pathways Responsible for Copper Metal Deposition

et al. 2010

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“…Cu–H elimination is well-documented 13,31,32, 33 and has been used in reaction development 34 . Through computational studies (Fig.…”

Section: Resultsmentioning

confidence: 99%

Mechanism-based enhancement of scope and enantioselectivity for reactions involving a copper-substituted stereogenic carbon centre

et al. 2017

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A rapidly emerging set of catalytic reactions involves intermediates that contain a copper-substituted stereogenic carbon centre. Here, we demonstrate that intimate understanding of this distinction provides ways for addressing limitations in reaction scope and explaining why unexpected variations in enantioselectivity often occur. By using catalytic enantioselective Cu–boryl addition to alkenes as the model process, we have been able to elucidate several key mechanistic principles. We show that higher electrophile concentration can lead to elevated enantioselectivity; this is because diastereoselective Cu–H elimination may be avoided and/or achiral Cu–boryl intermediates can be converted to allyl–B(pin) rather than add to an alkene. We illustrate that lower alkene amounts and/or higher chiral ligand concentration can minimize the deleterious influence of achiral Cu–alkyl species, resulting in improved enantiomeric ratios. Moreover, and surprisingly, we find that enantioselectivities are higher with the less reactive allylphenyl carbonates as chemoselective copper–hydride elimination is faster with an achiral Cu-alkyl species.

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“…The readily synthesized key substrate 24 underwent a copper-mediated C-C biaryl bond-forming reaction. Whitesides [64] and more recently Lipshutz and co-workers [65][66][67][68] applied oxidants to aryl cuprates to form biaryls intermolecularly. By adapting the experimental procedure of Schreiber and co-workers, [69] which allows the synthesis of a series of asymmetric biaryl-containing macrocyclic rings, the cyclononane structure 26 was synthesized successfully.…”

Section: Synthesismentioning

confidence: 99%

Synthesis of Rotationally Restricted and Modular Biphenyl Building Blocks

Vonlanthen¹,

Rotzler²,

Neuburger³

et al. 2009

Eur J Org Chem

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A series of modular biphenyl building blocks with stepwise adjusted torsion angles and terminally functionalized with leaving groups have been synthesized. The two phenyl rings of the biphenyl synthon are clamped by alkyl chains of various lengths. The desired building blocks 3 and 4 were obtained by copper-mediated C-C biaryl coupling reactions followed by the construction of interlinking alkyl bridges. The key intermediates 14 and 15 were transformed into the corresponding cycloheptadienones 16 and 17, which were reduced to the desired propyl-bridged biphenyls 3b and 3c. The butyl-bridged derivatives 4b and 4c were obtained from

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Mechanism of thermal decomposition of n-butyl(tri-n-butylphosphine) copper(I)

Cited by 117 publications

References 0 publications

Solution Reactions of a Bis(pyrrolylaldiminate)copper(II) Complex with Peralkyl Zinc, Aluminum, and Boron Reagents: Investigation of the Pathways Responsible for Copper Metal Deposition

Solution Reactions of a Bis(pyrrolylaldiminate)copper(II) Complex with Peralkyl Zinc, Aluminum, and Boron Reagents: Investigation of the Pathways Responsible for Copper Metal Deposition

Mechanism-based enhancement of scope and enantioselectivity for reactions involving a copper-substituted stereogenic carbon centre

Synthesis of Rotationally Restricted and Modular Biphenyl Building Blocks

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