Ligand-Dependent Scope and Divergent Mechanistic Behavior in Nickel-Catalyzed Reductive Couplings of Aldehydes and Alkynes

Mahandru, Gireesh M.; Liu, Gang; Montgomery, John

doi:10.1021/ja049644n

Cited by 230 publications

(39 citation statements)

References 25 publications

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“…[43][44][45] Auf diese ersten Arbeiten hin folgten bald intermolekulare Varianten der Nickel-katalysierten reduktiven Alkin-Carbonyl-Kupplungen. [37,46] Während nun stöchiometrische metallorganische Reagentien vermieden werden, sind andererseits terminale Reduktionsmittel wie Hydrosilane, Hydrostanna-ne, Organozinkreagentien, Organoborreagentien oder CrCl 2 nötig, die zu molaren ¾quivalenten von Nebenprodukten führen. Unter den Bedingungen der Rhodium-und Iridiumkatalysierten Hydrierung ist es dagegen möglich, reduktive Alkin-Carbonyl-und Imin-Carbonyl-Kupplungen mit hoher Regio-und Stereoselektivität ohne Bildung von Nebenprodukten durchzuführen (Schema 20).…”

Section: Methodsunclassified

Katalytische Carbonyladdition durch Transferhydrierung: weg von vorab gebildeten Organometallreagentien

et al. 2008

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Die klassischen Verfahren der Carbonylallylierung, ‐propargylierung und ‐vinylierung setzen auf die Verwendung von vorab gebildeten Allylmetall‐, Allenylmetall‐ bzw. Vinylmetallreagentien, was die Bildung stöchiometrischer Mengen an metallischen Nebenprodukten bedingt. Durch transferhydrierende C‐C‐Kupplung gelingt es jedoch, Carbonyladditionen auch ohne stöchiometrische Organometallreagentien oder metallische Reduktionsmittel auszuführen, wobei von einem Aldehyd oder Alkohol ausgegangen wird. In diesem Kurzaufsatz geben wir einen Überblick über Transferhydrierungsmethoden für die Carbonyladdition. Es handelt sich nebenbei um die ersten katalytischen Methoden, die eine direkte C‐H‐Funktionalisierung von Alkoholen ermöglichen.

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Section: Methodsunclassified

Katalytische Carbonyladdition durch Transferhydrierung: weg von vorab gebildeten Organometallreagentien

et al. 2008

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“…Later, Montgomery showed that reductive couplings could also be accomplished using N -heterocyclic carbene (NHC) ligands with trialkylsilanes as reducing agents. 6 …”

Section: Reductive Coupling Reactions Of Alkynesmentioning

confidence: 99%

Nickel Catalysis: Synergy between Method Development and Total Synthesis

et al. 2015

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Natural products are a continual source of inspiration for chemists, particularly for organic chemists engaged in reaction development and methodology. In the early stages of our research program, we were drawn to macrocyclic natural products containing allylic alcohol moieties, such as (−)-terpestacin (1, Figure 1). We envisioned, in an ideal case, an intramolecular reductive coupling (a field still in its infancy at the time) could be developed to join an alkyne and an aldehyde to yield this allylic alcohol, simultaneously closing the macrocycle. For this reason we began studying reductive coupling as a tool for C–C bond formation. Additionally, as our program developed, it became clear that a number of other natural products, such as amphidinolide T1 (2), which, although they do not contain allylic alcohols, could be produced in an analogous fashion after modification of the allylic alcohol formed from such a macrocyclization.

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“…33 Recent applications in nickel-catalysed reductive coupling reactions have further illustrated the influence of the ligand on both reaction mechanism and regioselectivity. 34,35 Montgomery examined the macrocyclization of 28 and found that when R 1 is phenyl, both phosphine and NHC ligands afford product 30; however, when R 1 is methyl, different regioselectivities were observed (Scheme 5). 33 Use of triethylborane as the reducing agent and PMe 3 as the ligand favoured formation of endocyclic product 29 (9:2 ratio), whereas a combination of IPr and triethylsilane led to predominant formation of the exocyclic double bond (5:1).…”

Section: Effect Of N-heterocyclic Carbene Ligandsmentioning

confidence: 99%

Regioselectivity and enantioselectivity in nickel-catalysed reductive coupling reactions of alkynes

2007

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Nickel-catalysed reductive coupling reactions of alkynes have emerged as powerful synthetic tools for the selective preparation of functionalized alkenes. One of the greatest challenges associated with these transformations is control of regioselectivity. Recent work from our laboratory has provided an improved understanding of several of the factors governing regioselectivity in these reactions, and related studies have revealed that the reaction mechanism can differ substantially depending on the ligand employed. A discussion of stereoselective transformations and novel applications of nickel catalysis in coupling reactions of alkynes is also included.

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Ligand-Dependent Scope and Divergent Mechanistic Behavior in Nickel-Catalyzed Reductive Couplings of Aldehydes and Alkynes

Cited by 230 publications

References 25 publications

Katalytische Carbonyladdition durch Transferhydrierung: weg von vorab gebildeten Organometallreagentien

Katalytische Carbonyladdition durch Transferhydrierung: weg von vorab gebildeten Organometallreagentien

Nickel Catalysis: Synergy between Method Development and Total Synthesis

Regioselectivity and enantioselectivity in nickel-catalysed reductive coupling reactions of alkynes

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