Taking Advantage of the Ambivalent Reactivity of Ynamides in Gold Catalysis: A Rare Case of Alkyne Dimerization

Kramer, Steven L.; Odabachian, Yann; Overgaard, Jacob; Rottländer, Mario; Gagosz, Fabien; Skrydstrup, Troels

doi:10.1002/anie.201100327

Cited by 109 publications

(35 citation statements)

References 44 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…(3)]. [6] In this context, and following our continuing interest in gold catalysis, [7,8] we considered the possibility of performing an alternative and unprecedented alkenyl nitrene transfer to alkynes [9] by taking advantage of the p-acid and electron-donor properties of gold complexes [Scheme 1, Eq. (4)].…”

mentioning

confidence: 99%

Gold‐Catalyzed Synthesis of Functionalized Pyridines by Using 2H‐Azirines as Synthetic Equivalents of Alkenyl Nitrenes

et al. 2014

Self Cite

View full text Add to dashboard Cite

2H-Azirines are easily synthesized from the corresponding ketones and, despite possessing a CN bond embedded in a strained three-membered cycle, they are sufficiently stable to be isolated, stored, and manipulated. 2H-Azirines can be regarded as valuable synthetic equivalents of alkenyl nitrenes, however, reactions capitalizing on the cyclic strain of the heterocyclic motif and involving the cleavage of the CN single bond remain surprisingly limited. A gold-catalyzed reaction that allows the formation of polysubstituted functionalized pyridines from easily accessible 2-propargyl 2H-azirine derivatives was developed. This transformation, which corresponds to an unprecedented intramolecular transfer of an alkenyl nitrene to an alkyne, proceeds with low catalyst loading, is efficient, and exhibits a high functional-group tolerance and a wide substrate scope.

show abstract

mentioning

confidence: 99%

Gold‐Catalyzed Synthesis of Functionalized Pyridines by Using 2H‐Azirines as Synthetic Equivalents of Alkenyl Nitrenes

et al. 2014

Self Cite

View full text Add to dashboard Cite

show abstract

“…18 It is tempting here to relate this result to aurophilicity, the sulfur affinity for gold surfaces that constitutes a central concept in heterogeneous catalysis. Yet, sulfur(s) interaction with an isolated transition‐metal element, cations or complexes may be very different: Au + is a much‐studied and versatile catalytic agent19–22 but, in spite of the amount of available data, we are still far from a complete understanding.…”

Section: Introductionmentioning

confidence: 99%

Unraveling Gold(I)‐Specific Action Towards Peptidic Disulfide Cleavage: A DFT Investigation

2011

View full text Add to dashboard Cite

Ground-state disulfide dissociation is a target of prime importance in structural biochemistry. A main difficulty consists in avoiding competition with carbon–sulfur and backbone scission pathways. In tandem mass spectrometry, such selectivity is afforded using transition elements or coinage-metal ions as catalyst. Yet, the underlying gas-phase mechanistic details remain poorly understood. Gold(I)-assisted disulfide cleavage is investigated by means of DFT calculations, to elucidate the highly selective and specific catalytic action of this transition-metal cation, a most promising one in tandem mass spectrometry. The preferential cleavage of sulfur–sulfur versus carbon–sulfur linkages on dimethyldisulfide, taken as a prototypical aliphatic compound, is rationalized on the basis of molecular orbital arguments. Secondly, it is revealed that the disulfide dissociation profile is dramatically impacted by a peptidic environment. Calculations on L,L-cystine derivatives show two main factors: the topological frustration for an embedded -CH(2)-S-S-CH(2)- motif induces a 5 kcal mol(-1) penalty, whereas electrophilic assistance via complexation of nitrogen and oxygen atoms lowers activation barriers by a factor of 3. S-S weakening is both thermodynamically and kinetically driven by the versatile coordination mode of gold(I). The influence of amine-terminus group protonation is finally sketched: it gives rise to an intermediate reactivity. This study sheds lights on the key action of the peptidic environment in tuning the dissociation profile in the presence of this transition-metal monocation.

show abstract

“…It provided an ew general access to functionalized 3 in one step under mild reaction conditions (30 8 8C), low substrate ratio (as low as equimolar), and low catalyst loading (1-4 mol %). It complements af ew shortcomings of the intramolecular approaches, [18] tailormade ynamides with Au vinyl carbenoids, [10,19] cycloaddition, [20] and approaches that use stoichiometric amounts of organometallic reagents. [21] High yield, functional-group compatibility,a nd regioselectivity (up to 46:1, > 20:1 in general) were noted in cases with either the commercially available or simple terminal alkynes 2 ( Table 2, Sets 1-3).…”

mentioning

confidence: 99%

[(NHC)Ni^IIH]‐Catalyzed Cross‐Hydroalkenylation of Cyclopropenes with Alkynes: Cyclopentadiene Synthesis by [(NHC)Ni^II]‐Assisted C−C Rearrangement

Huang

2019

Angewandte Chemie

View full text Add to dashboard Cite

Ac ross-hydroalkenylation/rearrangement cascade (HARC), using ac yclopropene and alkyne as substrate pairs, was achieved for the first time by using new [(NHC)Ni-(allyl)]BAr F catalysts (NHC = N-heterocyclic carbenes). By controlling the (NHC)Ni II Hr elative insertion reactivity with cyclopropene and alkyne,abroad scope of cyclopentadienes was obtained with highly selectively.The structural features of the new (NHC)Ni II catalyst were important for the success of the reaction. The mild reaction conditions employed may serve as an entry for exploring (NHC)Ni II -assisted vinylcyclopropane rearrangement reactivity.Cyclopropenes (1)are important building blocks in organic synthesis,a nd significant advances for their synthesis have been made recently by using new transition-metal catalysts. Other than the use of traditional methods, [1] catalysts like Au, [2] Rh, [3] Cu, [4] Zn, [5] Pt, [6] and Pd [7] are particularly useful in ring-opening reactions of 1. [8] Thei ntermediates,s uch as the reactive vinyl metal carbenoids and the cyclopropane ions,are often trapped by either nearby functional groups on the skeleton or external nucleophiles (Scheme 1a), providing ag eneral route to substituted furans,p yrans,a nd acyclic products.T ransition-metal hydride catalysts or their equivalents [9] could potentially be one of the most ideal approaches for cyclopropene functionalization since it could insert into the olefin and allow subsequent insertions of various reaction partners.However, their use in selective transformation of 1 is rarely reported. [7] An umber of other possible reactivities of 1 with transition-metal hydride lead to unfavorable consumption of 1,and have severely limited the progress of the crossreaction development. With either too high of an insertion activity of 1 or competing pathways from other reaction partners,such as the alkyne 2,the non-selective oligomerization or homoreaction reactivity often dominates (Scheme 1bi).M oreover,o ther possible rearrangements were reported as one of the possible pathways for allylÀNu formation, and that made the hydride approach even more complicated (Scheme 1bii).A sac onsequence,h ighly selec-tive cross-transformations of 1 by transition-metal hydride catalyst and external p systems [2b,3d, 4, 10] remains elusive. Oxidative addition followed by either rearrangement or trapping is still dominating the field in Ni-catalyzed threemembered ring opening (Scheme 1c). [11,12] Herein, across-hydroalkenylation/rearrangement cascade (HARC) of 1 and 2 is achieved for the first time by using an ew set of [(NHC)Ni(allyl)]BAr F catalysts (Scheme 1d; NHC = N-heterocyclic carbene). Unlike the cross-hydroalkenylation of two different alkenes, [9b,13, 14] it provides highly efficient access to synthetically valuable,functionalized cyclopentadienes (3)r ather than gem-olefins.I nstead of using oxidative addition conditions for three-membered ring opening by Ni 0 in Scheme 1c,t he CÀCb ond cleavage is possibly assisted by (NHC)Ni II in as ubsequent rearrangement under mild cond...

show abstract

Taking Advantage of the Ambivalent Reactivity of Ynamides in Gold Catalysis: A Rare Case of Alkyne Dimerization

Cited by 109 publications

References 44 publications

Gold‐Catalyzed Synthesis of Functionalized Pyridines by Using 2H‐Azirines as Synthetic Equivalents of Alkenyl Nitrenes

Gold‐Catalyzed Synthesis of Functionalized Pyridines by Using 2H‐Azirines as Synthetic Equivalents of Alkenyl Nitrenes

Unraveling Gold(I)‐Specific Action Towards Peptidic Disulfide Cleavage: A DFT Investigation

[(NHC)Ni^IIH]‐Catalyzed Cross‐Hydroalkenylation of Cyclopropenes with Alkynes: Cyclopentadiene Synthesis by [(NHC)Ni^II]‐Assisted C−C Rearrangement

Contact Info

Product

Resources

About

Taking Advantage of the Ambivalent Reactivity of Ynamides in Gold Catalysis: A Rare Case of Alkyne Dimerization

Cited by 109 publications

References 44 publications

Gold‐Catalyzed Synthesis of Functionalized Pyridines by Using 2H‐Azirines as Synthetic Equivalents of Alkenyl Nitrenes

Gold‐Catalyzed Synthesis of Functionalized Pyridines by Using 2H‐Azirines as Synthetic Equivalents of Alkenyl Nitrenes

Unraveling Gold(I)‐Specific Action Towards Peptidic Disulfide Cleavage: A DFT Investigation

[(NHC)NiIIH]‐Catalyzed Cross‐Hydroalkenylation of Cyclopropenes with Alkynes: Cyclopentadiene Synthesis by [(NHC)NiII]‐Assisted C−C Rearrangement

Contact Info

Product

Resources

About

[(NHC)Ni^IIH]‐Catalyzed Cross‐Hydroalkenylation of Cyclopropenes with Alkynes: Cyclopentadiene Synthesis by [(NHC)Ni^II]‐Assisted C−C Rearrangement