Synthesis of alkynamides through reaction of alkyl- or aryl-substituted alkynylaluminums with isocyanates

Cho, Soohong; Lee, Yeonjoo; Lee, Kyeongmin; Lee, Hwiwoong; Lee, Yun-Mi; Jung, Byunghyuck

doi:10.1039/d1ob01990b

“…The insertion of unsaturated molecules into the Al−Cp* bond has been recently reported by Cowley and co‐workers [34] . The insertion of the isocyanate into the Al−Ge bond of 4 is similar to the reaction pattern of alkynylaluminums with isocyanates that gives alkynamides [35] . The structure of 7 in the solid state shows a tricyclic skeleton incorporating one five‐membered AlC2GeSi ring and two four‐membered AlCGeN and CGe2O rings (Figure 3, right).…”

Section: Methodsmentioning

confidence: 54%

A Silylene‐Stabilized Germanium Analogue of Alkynylaluminum

Chen

¹

,

Lei

²

,

Wang

³

et al. 2022

Angewandte Chemie

4

0

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In contrast to the well-developed metal acetylides, the heavier analogues of the type REEM (E = Si, Ge, Sn, Pb; M = metals) have not been reported to date. Herein, we describe the synthesis of a silylenestabilized germanium analogue of alkynylaluminum ( 4) by the reaction of a silylene-stabilized digermavinylidene (3) with 0.25 equiv of (AlCp*) 4 in THF at 80 °C. The structure of 4 has been unambiguously characterized by spectroscopic analysis, X-ray diffraction analyses and DFT calculations, and features a linear AlGeGe skeleton with a Ge=Ge double bond and a polarized GeÀ Al bond. Complex 4 shows excellent reactivity towards small molecules such as H 2 , CS 2 and TolNCO, and this allows for the construction of the structurally intriguing germylenyl aluminum complex (5) and the germacycles (6, 7).

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“…[34] The insertion of the isocyanate into the AlÀ Ge bond of 4 is similar to the reaction pattern of alkynylaluminums with isocyanates that gives alkynamides. [35] The structure of 7 in the solid state shows a tricyclic skeleton incorporating one five-membered AlC2GeSi ring and two four-membered AlCGeN and CGe2O rings (Figure 3, right). The two four-membered rings are almost coplanar with a dihedral angle of 3.44°.…”

Section: Methodsmentioning

confidence: 99%

A Silylene‐Stabilized Germanium Analogue of Alkynylaluminum

Chen

¹

,

Lei

²

,

Wang

³

et al. 2022

View full text Add to dashboard Cite

In contrast to the well-developed metal acetylides, the heavier analogues of the type REEM (E = Si, Ge, Sn, Pb; M = metals) have not been reported to date. Herein, we describe the synthesis of a silylenestabilized germanium analogue of alkynylaluminum ( 4) by the reaction of a silylene-stabilized digermavinylidene (3) with 0.25 equiv of (AlCp*) 4 in THF at 80 °C. The structure of 4 has been unambiguously characterized by spectroscopic analysis, X-ray diffraction analyses and DFT calculations, and features a linear AlGeGe skeleton with a Ge=Ge double bond and a polarized GeÀ Al bond. Complex 4 shows excellent reactivity towards small molecules such as H 2 , CS 2 and TolNCO, and this allows for the construction of the structurally intriguing germylenyl aluminum complex (5) and the germacycles (6, 7).

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“…Due to the large relevance of propiolamides, several synthetic strategies have been developed recently for their preparation including non-catalytic methodologies [20][21][22][23][24][25][26][27] that, although can be practical, are not efficient from the viewpoint of atom economy. Regarding catalytic methods, protocols employing amide-based compounds, [28][29][30][31][32] isocyanates [33] or isocyanides [34][35] have been also explored in the presence of homogeneous catalytic systems. In addition, several photocatalytic processes [36][37][38][39] or catalytic methodologies involving pre-functionalized alkynes [40][41][42] have been reported.…”

Section: Introductionmentioning

confidence: 99%

A General and Highly Versatile Heterogeneous Pd‐Catalyzed Oxidative Aminocarbonylation of Alkynes with Aromatic and Aliphatic Amines

Arango‐Daza,

Cabrero‐Antonino,

Adam

2024

ChemSusChem

0

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An efficient heterogeneous catalytic system for the oxidative aminocarbonylation of alkynes and amines in the presence of CO/O2 to afford substituted propiolamides has been developed. The active nanocatalyst, [Pd/Mg3Al‐LDH]‐300(D), is composed by Pd nanoaggregates (2‐3 nm average particle size) stabilized over a partially dehydrated [Mg3Al‐LDH] matrix. The methodology has resulted widely applicable, being the first catalytic system, either homogeneous or heterogeneous, able to activate not only aliphatic amines but also poorly‐nucleophilic aromatic amines. In fact, >60 substituted propiolamides have been synthesized in good to excellent isolated yields through this methodology, being 27 novel compounds. An important characterization effort (XRD, 27Al MAS NMR, TGA, TPD‐CO2, BET area, XPS, HAADF‐HRSTEM and HRTEM) and optimization of the synthesis conditions of the optimal catalyst has been performed. This study, together with a series of kinetic and mechanistic essays, indicates that the optimal catalyst is composed by Pd(0) species stabilized in a partially dehydrated/dehydroxylated LDH material with a Mg/Al molar ratio of 3 and a small crystallite size. All the experimental data indicates that the in situ formation of [PdI2] active species in the material surface together with the presence of a matrix with the optimal acid/base properties are key aspects of this process.

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Synthesis of alkynamides through reaction of alkyl- or aryl-substituted alkynylaluminums with isocyanates

Abstract: A broad range of alkynamides were efficiently synthesized through Et3N-catalyzed alumination of terminal alkynes with AlMe3, followed by nucleophilic addition of alkynylaluminums to isocyanates.

Cited by 10 publications

References 62 publications

A Silylene‐Stabilized Germanium Analogue of Alkynylaluminum

A Silylene‐Stabilized Germanium Analogue of Alkynylaluminum

A Silylene‐Stabilized Germanium Analogue of Alkynylaluminum

A General and Highly Versatile Heterogeneous Pd‐Catalyzed Oxidative Aminocarbonylation of Alkynes with Aromatic and Aliphatic Amines

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