Ligand-controlled stereodivergent alkenylation of alkynes to access functionalized trans- and cis-1,3-dienes

Long, Tianyu; Zhu, Chen; Li, Ling; Shao, Lei; Zhu, Shuaishuai; Rueping, Magnus; Chu, Lingling

doi:10.1038/s41467-022-35688-2

Cited by 44 publications

(10 citation statements)

References 78 publications

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“…Alkynes, as active electrophiles, are commonly used as coupling partners in nickel-catalyzed reductive coupling three-component reactions . In 2015, Huang’s group used B 2 pin 2 as the environmentally friendly reducing agent to realize the reductive tetramerization of alkynes under nickel catalysis .…”

Section: Nickel-catalyzed Diboron-promoted Reductive Coupling Reactionsmentioning

confidence: 99%

Recent Progress in Transition-Metal-Catalyzed Reductive Cross-Coupling Reactions Using Diboron Reagents as Reductants

Geng,

Shi,

Guo

et al. 2023

ACS Catal.

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Transition-metal-catalyzed reductive cross-coupling reactions have been developed as one of the important tools for constructing C−C bonds. These reactions involve the direct coupling of two distinct electrophiles promoted by transition metals and reductants. Notably, these methods offer advantages over conventional cross-coupling reactions because they circumvent the need for air-and moisture-sensitive organometallic reagents while being simple to operate and exhibiting good compatibility with various functional groups. In recent years, diboron reagents have gained prominence as reductants for reductive cross-coupling reactions alongside traditional metal reductants, such as Zn, Mn, and Mg. This Review aims to provide an insightful overview of nickel/copper/iron-catalyzed reductive coupling reactions using diboron reagents as reductants and illustrate their possible reaction mechanisms.

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Section: Nickel-catalyzed Diboron-promoted Reductive Coupling Reactionsmentioning

confidence: 99%

Recent Progress in Transition-Metal-Catalyzed Reductive Cross-Coupling Reactions Using Diboron Reagents as Reductants

Geng,

Shi,

Guo

et al. 2023

ACS Catal.

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“…In recent years, mild radical‐involved organic transformations, [12, 4h] especially those via electrochemistry, [13] have emerged as versatile and powerful tools for the efficient construction of chemical bonds in a greener and more sustainable manner. Notably, a series of challenging electrochemical cross‐electrophile couplings have been realized by Lin, [14] Sevov, [15] Gosmini, [16] and others [17] .…”

Section: Introductionmentioning

confidence: 99%

Group 14 Elements Hetero‐Difunctionalizations via Nickel‐Catalyzed Electroreductive Cross‐Coupling

et al. 2023

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The difunctionalization of unsaturated bonds plays a vital role in the enrichment of molecular complexity. While various catalytic methods for alkene and alkyne difunctionalization have been developed in recent years, hetero‐functionalization the introduction of two different atoms has been less explored. This is mainly due to the challenges associated with achieving high chemo‐, regio‐, and stereoselectivity, especially when adding two similar atoms from the same group across unsaturated bonds. In this study, we describe a nickel‐catalyzed, three‐component reductive protocol for group 14 element hetero‐difunctionalization of 1,3‐enynes using electrochemistry. This new method is mild, selective, and general, allowing for the silyl‐, germanyl‐, and stannyl‐alkylation of enynes. Various chlorosilanes as well as chlorogermans, and chlorostannanes can be successfully used in combination with aryl/alkyl‐substituted 1,3‐enynes and primary, secondary, and tertiary alkyl bromides in the electroreductive coupling.

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“…In addition to traditional homolytic bond cleavage-based radical reactions induced by radical initiators or photolysis [ 15 , 16 , 17 ], other methods such as single electron transfer reagents [ 18 , 19 , 20 , 21 , 22 ], catalytic photoredox [ 23 , 24 , 25 , 26 , 27 , 28 ], and electrochemical reactions [ 29 , 30 , 31 , 32 , 33 , 34 , 35 ] have been developed and are gaining increasing popularity. For the remote 1,3-, 1,4-, 1,5-, 1,6- and 1,7-difunctionalization reactions presented in this paper, the initial addition of the radical X is followed by radical rearrangement through resonance, hydrogen atom transfer (HAT), group transfer, or opening of strained-rings to relocate the position of the radical.…”

Section: Introductionmentioning

confidence: 99%

Remote Radical 1,3-, 1,4-, 1,5-, 1,6- and 1,7-Difunctionalization Reactions

Zhang

2023

Molecules

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Radical transformations are powerful in organic synthesis for the construction of molecular scaffolds and introduction of functional groups. In radical difunctionalization reactions, the radicals in the first functionalized intermediates can be relocated through resonance, hydrogen atom or group transfer, and ring opening. The resulting radical intermediates can undertake the following paths for the second functionalization: (1) couple with other radical groups, (2) oxidize to cations and then react with nucleophiles, (3) reduce to anions and then react with electrophiles, (4) couple with metal-complexes. The rearrangements of radicals provide the opportunity for the synthesis of 1,3-, 1,4-, 1,5-, 1,6-, and 1,7-difunctionalization products. Multiple ways to initiate the radical reaction coupling with intermediate radical rearrangements make the radical reactions good for difunctionalization at the remote positions. These reactions offer the advantages of synthetic efficiency, operation simplicity, and product diversity.

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Ligand-controlled stereodivergent alkenylation of alkynes to access functionalized trans- and cis-1,3-dienes

Cited by 44 publications

References 78 publications

Recent Progress in Transition-Metal-Catalyzed Reductive Cross-Coupling Reactions Using Diboron Reagents as Reductants

Recent Progress in Transition-Metal-Catalyzed Reductive Cross-Coupling Reactions Using Diboron Reagents as Reductants

Group 14 Elements Hetero‐Difunctionalizations via Nickel‐Catalyzed Electroreductive Cross‐Coupling

Remote Radical 1,3-, 1,4-, 1,5-, 1,6- and 1,7-Difunctionalization Reactions

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