A new class of organocopper and organocuprate compounds derived from copper(I) arenethiolates

Knotter, D. Martin; Grove, David M.; Smeets, Wilberth J. J.; Spek, Anthony L.; Koten, Gerard van

doi:10.1021/ja00035a036

Cited by 115 publications

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“…the tri-nuclear aggregate Cu 3 (SC 6 H 4 CHMeNMe 2 -2) 3 (abbr. as Cu 3 (SAr*) 3 ) [33,34]. The idea was that the stereoselectivity of copper catalyzed cross-coupling reactions of, e.g.…”

Section: 2mentioning

confidence: 99%

“…23 was selectively formed by mixing mesitylcopper and copper aminoarenethiolate in 1:1 M ratio and then transferred to 23 by addition of one equivalent of PPh 3 (mimicking the addition of an electrophilic substrate to the cuprate intermediate), see Fig. 12 [33,35]. To summarize: the reaction of MgIMe with a diethyl ether solution of benzylideneacetone and 3 mol% of [CuSAr*] (providing the "dummy", non-transferable anion), at 0 C gives rise to the formation of the 1,4-addition product in 57% ee [33,35,36].…”

Section: 2mentioning

confidence: 99%

“…12 [33,35]. To summarize: the reaction of MgIMe with a diethyl ether solution of benzylideneacetone and 3 mol% of [CuSAr*] (providing the "dummy", non-transferable anion), at 0 C gives rise to the formation of the 1,4-addition product in 57% ee [33,35,36]. This preliminary result (later improved to 76%) represented, to the best of our knowledge, one of the first reported examples of the catalytic use of a copper salt with a chiral auxiliary in an enantioselective 1,4-addition reaction of self-assembled cuprate reagents.…”

Section: 2mentioning

confidence: 99%

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Highlights of 45 years of research: A personal account

Koten

2017

Journal of Organometallic Chemistry

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a b s t r a c tThis part of my biosketch, which I prepared on invitation by the Editors, made me realize again how entangled my interest for doing research and teaching and management have been over the years. Working together with my students and colleagues has always been a strong motivation and pleasure for me and I hope that this sketch of our research reflects our common enthusiasm for what we achieved.In hindsight, trying to overlook almost 45 years of research, various main themes can be discerned that marked my fundamental research in the subsequent periods at TNO Utrecht (1968e1977), University of Amsterdam (1977e1986) and University of Utrecht (1986e2007). Overarching has been my preference and fascination for working with nitrogen based ligands (culminating in the design and use of the NCNpincer ligand platform, vide infra), the study of synthetic routes for organometallics (most importantly trans-and cyclo-metallation routes), the use of NMR for the study of the stereochemistry of organometallics (cf. the early use of 107,109 Ag NMR for detecting and following the formation of coordination compounds with helical structures), chemistry involving organometallic radicals (cf. organozinc and aluminum a-diimine chemistry, development of b-lactam synthesis routes), self-assembly of organometallics to discrete aggregated species (cf. organo-Cu, -Li and cuprate chemistry), the development of palladium complexes and homogeneous metal catalysts with simple amine ligands, the synthesis of, and catalysis with, dendrimers decorated with organometallic catalysts, mimicking the active center of metallo-enzymes as well as the synthesis of organometal-lipase hybrids for catalysis.Being educated in an "eco"-system of contract research, in concert with fundamental research, the results of the above outlined items were not only published in journals with peer review (>850) but also in the patent literature (>40). Most important were the results reported in over 85 PhD theses that I had the privilege to supervise as PI. The references refer to key-papers describing this body of work. The respective reference numbers are given at the heading of each paragraph. The full list of publications in peer reviewed Journals can be found in http://www.gerardvankoten.nl and www.uu.nl/staff/GvanKoten.© 2017 The Author. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/). GeneralAs indicated above, nitrogen ligands fascinated me throughout my research career, right from the very beginning. Whereas in my early days ligands with phosphorous donor atoms were the dominating "privileged" ligands in inorganic and organometallic chemistry; they have remained so up until now. However, my interest for nitrogen-containing ligands was fortified for a number of reasons; i, Nitrogen is one of the smallest donor atoms. This results in short N-metal bond distances thus affecting/interfering with its (N)R-substituents (also because of the short N-C bonds, viz. N-cone angle c...

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“…the tri-nuclear aggregate Cu 3 (SC 6 H 4 CHMeNMe 2 -2) 3 (abbr. as Cu 3 (SAr*) 3 ) [33,34]. The idea was that the stereoselectivity of copper catalyzed cross-coupling reactions of, e.g.…”

Section: 2mentioning

confidence: 99%

Section: 2mentioning

confidence: 99%

Section: 2mentioning

confidence: 99%

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Highlights of 45 years of research: A personal account

Koten

2017

Journal of Organometallic Chemistry

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“…Shortly after this seminal work was published, various catalytic systems were developed based on copper thiolates (24)(25)(26)(27)(28)(29)(30) and monophosphine ligands (31)(32)(33)(34), although in these systems, enantioselectivities rarely reached the 90% enantiomeric excess (ee) level. Notable exceptions are the two literature reports of 92% ee in the addition of BuMgCl to cyclic enones.…”

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confidence: 99%

“…In principle, diphosphines do not match with the metal-differentiating coordination concept (32). It should be emphasized that until now, most successful ligands in the field of copper-catalyzed 1,4-addition of Grignard reagents fulfill the criteria of combining P, S, or Se with N or O donor atoms in their structure to coordinate selectively with Cu and Mg of the organometallic species, respectively (24)(25)(26)(27)(28)(29)(30)(31)(32)(33)(34). Among the most important bidentate ligands in asymmetric catalysis are ferrocenyl diphosphine ligands, especially TaniaPhos (1; Fig.…”

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confidence: 99%

Copper-catalyzed asymmetric conjugate addition of Grignard reagents to cyclic enones

Feringa

Badorrey²,

Peña³

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

138

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It is no longer necessary to use dialkylzinc reagents to obtain enantioselectivities >95% in the copper-catalyzed asymmetric conjugate addition of organometallic compounds to cyclic enones. We now report how this can be accomplished by using inexpensive and readily available Grignard reagents. Screening of bidentate ligands provided outstanding results with copper complexes of commercially available chiral ferrocenyl-based diphosphines, in particular TaniaPhos and JosiPhos derivatives. These catalysts tolerate a range of Grignard reagents and different cyclic enones as substrates, leading to high regioselectivities and unprecedented enantioselectivities. Moreover, the reactions are successful with moderate catalyst loading (5 mol %) under mild conditions and in the absence of additives.

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