Copper-Catalyzed Intermolecular Generation of Ammonium Ylides with Subsequent [2,3]Sigmatropic Rearrangement. Efficient Synthesis of Bifunctional Homoallylamines

Honda, Kiyoshi; Shibuya, Hiromasa; Yasui, Hiroto; Hoshino, Yujiro; Inoue, Seiichi

doi:10.1246/bcsj.81.142

Cited by 19 publications

(6 citation statements)

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“…[15] In situ prepared allyl ammonium ylide adducts of Cu and Zn have been used in [2,3] rearrangements,b ut no cyclopropanation derived from the ylides was observed. [16] Nevertheless,t he behavior of Ni 0 as aw eak Lewis acid (the L 2 Ni 0 fragment is isolobal to DCH 2 )h as been studied in detail. Pçrschke et al reported the addition of MeLi and Ph 3 PCH 2 to Ni 0 to give the corresponding niccolates(0) (Figure 2).…”

Section: Methodsmentioning

confidence: 99%

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ChemInform Abstract: Nickel‐Catalyzed Cyclopropanation with NMe₄OTf and nBuLi.

Kuenzi¹,

Toro²,

Hartog³

et al. 2016

ChemInform

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Nickel was identified as ac atalyst for the cyclopropanation of unactivated olefins by using in situ generated lithiomethyl trimethylammonium triflate as amethylene donor. Am echanistic hypothesis is proposed in which the generation of ar eactive nickel carbene explains several interesting observations.A dditionally,o ur findings shed light on ar eport by Franzen and Wittigp ublished in 1960 that had been retracted later owingt oi rreproducibility,a nd provide arational basis for the systematic development of the reaction for preparative purposes as an alternative to diazomethane or Simmons-Smith conditions. In1960, in as hort Communication in Angewandte Chemie, Franzen and Wittig reported the cyclopropanation of cyclohexene with tetramethylammonium bromide (1)t og ive norcarane (2).[1] Dropwise addition of an ethereal solution of phenyllithium/phenylsodium (1:10) to asuspension of 1 in neat cyclohexene resulted in the formation of 2 in 5-18 % yield. Franzen and Wittig proposed the decomposition of trimethylammonium methylide into af ree carbene that is trapped by cyclohexene to give 2.In1964, in Liebigs Annalen, Wittig and Krauss reported that the 1960 cyclopropanation could not be reproduced under any conditions,and explicitly retracted the earlier claim.[2] Since then, this verdict has seemingly remained unchallenged;t here have been no published reports of any attempts to use tetramethylammonium salts as methylene donors and no citations of the work.[3]Herein, we report the nickel-catalyzed cyclopropanation of unactivated olefins with tetramethylammonium triflate and nBuLi, which suggests that Franzens work on cyclopropanation might have worked after all, albeit with the unsuspected influence of am etal catalyst. Moreover,w er eport unusual features of the reaction that would have hindered reproduction of the original work.There are only afew methods for the cyclopropanation of electron-rich olefins known, especially for simple methylenation. TheSimmons-Smith reaction is the method of choice in industry but has the drawback of generating alarge amount of waste.[4] Thed ecomposition of diazomethane with transition metals,a lthough very versatile,i sl imited to small-scale reactions owing to the inherent hazards of the reagent itself.[5, 6] As afe,s calable,a nd cost-effective method for these substrates would therefore be highly desirable.Our group recently reported the addition of lithiomethyl trimethylammonium triflate to unsaturated bonds to give aziridines,e poxides,a nd cyclopropanes. [7,8] Even though styrenes and stilbenes could be cyclopropanated in good to excellent yields,t he substrate scope was limited to these activated alkenes;attempts to cyclopropanate an unactivated olefin, cyclohexene,r esulted only in recovery of the starting material.We report now that avariety of nickel complexes catalyze the cyclopropanation of unactivated olefins.Inthe absence of catalyst, no reaction takes place (Table 1, entry 1). Different nickel sources,w ith and without added phosphine ligands, proved to be...

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Section: Methodsmentioning

confidence: 99%

“…. 16 b (Figure 4). [26] Both undergo facile reductive elimination to form the corresponding cyclopropanes in quantitative yield.…”

Section: Methodsmentioning

confidence: 99%

ChemInform Abstract: Nickel‐Catalyzed Cyclopropanation with NMe₄OTf and nBuLi.

Kuenzi¹,

Toro²,

Hartog³

et al. 2016

ChemInform

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“…For example, both halogen-substituted and methoxy-substituted phenyl derivatives were synthesized in good yields with high diastereomeric ratios. The reaction conditions also tolerated heterocycles with a Lewis basic pyridine functionality (entry 7), which may be especially problematic for protocols mediated by Lewis acids or metal carbenoids . Since aliphatic substituents did not impact the reaction efficiency (entry 8), this method may provide access to a diverse array of unnatural amino acid derivatives.…”

mentioning

confidence: 65%

“…Unfortunately, the broad application of these rearrangements has not been fully realized because of the difficulties associated with synthesizing and isolating many ammonium salt precursors. , The development of a mild and general metal-catalyzed tandem ammonium ylide generation/[2,3]-rearrangement would obviate the need to synthesize and isolate these reactive intermediates. While metal carbenoid-mediated couplings between tertiary allylic amines and diazoesters represent the most successful catalytic strategy for generating ammonium ylides, the challenge of synthesizing diazoesters with diverse functionalities reduces the potential scope of this approach …”

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confidence: 99%

Tandem Catalytic Allylic Amination and [2,3]-Stevens Rearrangement of Tertiary Amines

Soheili

Tambar

2011

J. Am. Chem. Soc.

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We have developed a catalytic allylic amination involving tertiary aminoesters and allylcarbonates, which is the first example of the use of tertiary amines as intermolecular nucleophiles in metal-catalyzed allylic substitution chemistry. This process is employed in a tandem ammonium ylide generation/[2,3]-rearrangement reaction, which formally represents a palladium-catalyzed Stevens rearrangement. Low catalyst loadings and mild reaction conditions are compatible with an unprecedented substrate scope for the ammonium ylide functionality, and products are generated in high yields and diastereoselectivities. Mechanistic studies suggested the reversible formation of an ammonium intermediate.

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“…[15] In situ hergestellte Allylammoniumylid-Addukte an Cu und Zn wurden in [2,3]-Umlagerungen verwendet, aber keine Cyclopropanierung ausgehend vom Ylid wurde beobachtet. [16] Dennoch wurde das Verhalten von Ni 0 als schwache LewisSäure (das L 2 Ni 0 -Fragment ist isolobal zu DCH 2 )i mDetail studiert. Pçrschke et al berichteten über die Addition von MeLi und Ph 3 PCH 2 an Ni 0 ,u md ie entsprechenden Niccolate(0) zu erhalten.…”

Section: Methodsunclassified

Nickel‐katalysierte Cyclopropanierung mit NMe₄OTf und nBuLi

et al. 2015

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[2] Dieses Urteil von damals scheint unangefochten geblieben;k eine Berichte über den Versuch, Te tramethylammoniumsalze als Methylendonoren zu verwenden, und keine Zitierungen der Arbeit wurden publiziert.[3] Hier berichten wir über die Nickel-katalysierte Cyclopropanierung von unaktivierten Olefinen mit Te tramethylammoniumtriflat und nBuLi, welche nahelegt, dass Franzens Cyclopropanierung tatsächlich funktioniert haben kçnnte,obgleich mit dem unvermuteten Einfluss eines Metallkatalysators.Z udem berichten wir über ungewçhnliche Eigenschaften der Reaktion, welche die Reproduzierung der ursprünglichen Arbeit verhindert haben kçnnten.Es sind nur wenige Methoden zur Cyclopropanierung von elektronenreichen Olefinen bekannt, besonders für einfache Methylenierungen. Die Simmons-Smith-Reaktion ist die bevorzugte Methode der Industrie,h at aber den Nachteil, dass sie große Mengen an Abfall generiert.[4] Die Zersetzung von Diazomethan mittels Übergangsmetallen, obwohl sehr vielseitig,i st wegen der inhärenten Gefahr des Reagens auf kleine Maßstäbe beschränkt. [5,6] Eine sichere,skalierbare,und kosteneffektive Methode für diese Substrate wäre deshalb sehr wünschenswert.Unsere Arbeitsgruppe berichtete kürzlich über die Addition von Lithiomethyltrimethylammoniumtriflat an ungesättigte Bindungen, um Aziridine,E poxide und Cyclopropane zu erhalten. [7,8] -Komplex (Einträge 3u nd 4). Überra-schenderweise lieferte kein anderer getesteter Metallkatalysator (Fe, Co,C u, Zn, Rh, Pd, Re) das Cyclopropanierungsprodukt in signifikanter Ausbeute,w as darauf hinweist, dass Nickel einzigartig für diese Reaktion ist (Tabelle S2 in den Hintergrundinformationen).Tabelle 2zeigt, dass die Ausbeute der Cyclopropanierung elektronenreicher Olefine die Neigung des Substrats zur Bildung eines Olefin-p-Komplexes widerspiegelt.[9] Basierend

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Copper-Catalyzed Intermolecular Generation of Ammonium Ylides with Subsequent [2,3]Sigmatropic Rearrangement. Efficient Synthesis of Bifunctional Homoallylamines

Cited by 19 publications

References 39 publications

ChemInform Abstract: Nickel‐Catalyzed Cyclopropanation with NMe₄OTf and nBuLi.

ChemInform Abstract: Nickel‐Catalyzed Cyclopropanation with NMe₄OTf and nBuLi.

Tandem Catalytic Allylic Amination and [2,3]-Stevens Rearrangement of Tertiary Amines

Nickel‐katalysierte Cyclopropanierung mit NMe₄OTf und nBuLi

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Copper-Catalyzed Intermolecular Generation of Ammonium Ylides with Subsequent [2,3]Sigmatropic Rearrangement. Efficient Synthesis of Bifunctional Homoallylamines

Cited by 19 publications

References 39 publications

ChemInform Abstract: Nickel‐Catalyzed Cyclopropanation with NMe4OTf and nBuLi.

ChemInform Abstract: Nickel‐Catalyzed Cyclopropanation with NMe4OTf and nBuLi.

Tandem Catalytic Allylic Amination and [2,3]-Stevens Rearrangement of Tertiary Amines

Nickel‐katalysierte Cyclopropanierung mit NMe4OTf und nBuLi

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ChemInform Abstract: Nickel‐Catalyzed Cyclopropanation with NMe₄OTf and nBuLi.

ChemInform Abstract: Nickel‐Catalyzed Cyclopropanation with NMe₄OTf and nBuLi.

Nickel‐katalysierte Cyclopropanierung mit NMe₄OTf und nBuLi