Copper‐Catalyzed Selective Semihydrogenation of Terminal Alkynes with Hypophosphorous Acid

Cao, Huanyang; Chen, Tieqiao; Zhou, Yongbo; Han, Daoqing; Yin, Shuang‐Feng; Han, Li‐Biao

doi:10.1002/adsc.201300916

Cited by 46 publications

(25 citation statements)

References 32 publications

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“…Cao's group reported a novel selective semihydrogenation of terminal alkynes, catalyzed by copper in the presence of H 3 PO 2 as hydrogen donor. 11 The reaction took place with high selectivity so that over-reduction products of ethylbenzene were not detected. The employment of fully deuterated hypophosphorous acid (D 3 PO 2 ) showed the distribution of deuterium incorporation in the alkenes.…”

Section: (F) Selective Semihydrogenation Of Terminal Alkynesmentioning

confidence: 99%

Hypophosphorous Acid

Gao

2014

Synlett

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Kai Gao was born in 1987 and raised in Huanggang City, Hubei Province, China. He received his degree in chemistry from Hubei University of Science and Technology in 2012. Currently, he is carrying out research under the supervision of Prof. Bo Yang and Dr. Xiali Liao at the Kunming University of Science and Technology. His research focuses on the synthesis of novel phosphoramide ligands and small molecules with important bioactivities.

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Section: (F) Selective Semihydrogenation Of Terminal Alkynesmentioning

confidence: 99%

Hypophosphorous Acid

Gao

2014

Synlett

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“…By comparing the performance, the broad scope, and the environmental friendliness of our Pd 0 ‐AmP‐HSN/DMSO system, it can be concluded that it compares favorably to many of the recently developed catalytic protocols for the partial reduction of alkynes. For example, it has the advantage of affording high yields of alkenes under milder reaction conditions, whereas other catalytic systems require higher catalyst loadings,– higher H 2 pressures, and elevated reaction temperatures . Particularly noteworthy in this regard is that our catalytic system is comparable in performance to a number of homogenous Pd protocols .…”

Section: Resultsmentioning

confidence: 98%

“…Moreover, Pd 0 ‐AmP‐HSN offers a more straight‐forward separation and recycling of catalyst without any compromise in activity, which is typically seen upon heterogenization. The ability of the current protocol to operate efficiently by using H 2 and DMSO makes it an atom‐efficient and green alternative to other catalytic systems using more environmentally harmful reductants– and poisoning agents …”

Section: Resultsmentioning

confidence: 99%

Application of Pd Nanoparticles Supported on Mesoporous Hollow Silica Nanospheres for the Efficient and Selective Semihydrogenation of Alkynes

et al. 2016

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Herein, the preparation of a heterogeneous catalyst consisting of 1–2 nm sized Pd nanoparticles supported on amino‐functionalized mesoporous hollow silica nanospheres and its use for the semihydrogenation of mono‐ and disubstituted alkynes is reported. By utilizing this Pd nanocatalyst together with the green poisoning agent DMSO, high yields of the desired alkenes could be achieved, while suppressing the degree of over‐reduction to alkanes. To our delight, the Pd nanocatalyst displayed remarkable chemoselectivity towards the alkyne moiety, allowing the transformation to be carried out in the presence of other reducible functionalities, such as halogens, carbonyl, and nitro groups.

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“…In a related process, terminal alkynes 23 (which are not tolerated by the abovementioned protocol based on ammonia borane) could be converted into the corresponding terminal alkenes 24 by employing hypophosphorous acid as the H 2 equivalent, while internal alkynes remained intact (Scheme 4, c). 41 As a much more practical and ready available H 2 equivalent, it was recently shown that iso-propanol can also be employed in copper(I)-catalyzed transfer hydrogenations. 42 With a simple NHC/copper(I) complex 22 in catalytic amounts and NaOtBu as a basic additive, internal alkynes 20 could be converted into Z-alkenes 21 in moderate to very good yield (48-96%), while maintaining a high to excellent Z/E ratio (82:18 to 99:1) (Scheme 4, b).…”

Section: Homogeneous Copper-catalyzed Transfer Hydrogenationsmentioning

confidence: 99%

Catch It If You Can: Copper-Catalyzed (Transfer) Hydrogenation Reactions and Coupling Reactions by Intercepting Reactive Intermediates Thereof

Brechmann

Teichert²

2020

Synthesis

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The key reactive intermediate of copper(I)-catalyzed alkyne semihydrogenations is a vinylcopper(I) complex. This intermediate can be exploited as a starting point for a variety of trapping reactions. In this manner, an alkyne semihydrogenation can be turned into a dihydrogen-mediated coupling reaction. Therefore, the development of copper-catalyzed (transfer) hydrogenation reactions is closely intertwined with the corresponding reductive trapping reactions. This short review highlights and conceptualizes the results in this area so far, with H2-mediated carbon–carbon and carbon–heteroatom bond-forming reactions emerging under both a transfer hydrogenation setting as well as with the direct use of H2. In all cases, highly selective catalysts are required that give rise to atom-economic multicomponent coupling reactions with rapidly rising molecular complexity. The coupling reactions are put into perspective by presenting the corresponding (transfer) hydrogenation processes first.1 Introduction: H2-Mediated C–C Bond-Forming Reactions2 Accessing Copper(I) Hydride Complexes as Key Reagents for Coupling Reactions; Requirements for Successful Trapping Reactions 3 Homogeneous Copper-Catalyzed Transfer Hydrogenations4 Trapping of Reactive Intermediates of Alkyne Transfer Semihydrogenation Reactions: First Steps Towards Hydrogenative Alkyne Functionalizations 5 Copper(I)-Catalyzed Alkyne Semihydrogenations6 Copper(I)-Catalyzed H2-Mediated Alkyne Functionalizations; Trapping of Reactive Intermediates from Catalytic Hydrogenations6.1 A Detour: Copper(I)-Catalyzed Allylic Reductions, Catalytic Generation of Hydride Nucleophiles from H2 6.2 Trapping with Allylic Electrophiles: A Copper(I)-Catalyzed Hydroallylation Reaction of Alkynes 6.3 Trapping with Aryl Iodides7 Conclusion

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Copper‐Catalyzed Selective Semihydrogenation of Terminal Alkynes with Hypophosphorous Acid

Cited by 46 publications

References 32 publications

Hypophosphorous Acid

Hypophosphorous Acid

Application of Pd Nanoparticles Supported on Mesoporous Hollow Silica Nanospheres for the Efficient and Selective Semihydrogenation of Alkynes

Catch It If You Can: Copper-Catalyzed (Transfer) Hydrogenation Reactions and Coupling Reactions by Intercepting Reactive Intermediates Thereof

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