Reactivity of Cyclic (Alkyl)(amino)carbenes (CAACs) and Bis(amino)cyclopropenylidenes (BACs) with Heteroallenes: Comparisons with their <i>N</i>‐Heterocyclic Carbene (NHCs) Counterparts

Kuchenbeiser, Glenn; Soleilhavoup, Michèle; Donnadieu, Bruno; Bertrand, Guy

doi:10.1002/asia.200900338

Cited by 47 publications

(38 citation statements)

References 77 publications

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“…N-Heterocyclic carbenes B and cyclic (alkyl)(amino)carbenes C afford betaines in the reaction with CO 2 and CS 2 . [10] After bubbling dry CO 2 gas through a toluene solution of 1 at room temperature, the 31 P NMR spectrum revealed a new resonance at d = À26.9 ppm, and the IR spectrum displayed a characteristic sharp absorption for isocyanates at 2262 cm…”

Section: Mecnmentioning

confidence: 99%

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Reactivity of a Stable Phosphinonitrene towards Small Molecules

Dielmann

Bertrand

2014

Chemistry A European J

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The room-temperature stable phosphinonitrene 1 undergoes a thermal rearrangement into heterocycle 2 through a process involving a nitrene insertion into a CH bond. In the presence of acetonitrile, a nitrene-acetonitrile adduct has been isolated; then it first rearranges into a ketenimine and subsequently into a rare example of diazaphosphete. Compound 1 also splits water, carbon dioxide, carbon disulfide, and elemental sulfur, although it reacts with white phosphorus, leading to a P5 N cluster formally resulting from the insertion of the PN moiety into a P-P edge of the P4 tetrahedron.

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Section: Mecnmentioning

confidence: 99%

“…For example, carbenes B and C are known to react with CO 2 , [10] CS 2 , [10] and P 4 . [11] The more nucleophilic and electrophilic carbenes C even react with CO, [12] H 2 , and NH 3 [13] to give the corresponding adducts, whereas NHCs B are inert under the same conditions.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of a Stable Phosphinonitrene towards Small Molecules

Dielmann

Bertrand

2014

Chemistry A European J

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“…最近, 通过测定卡宾与 CO 2 或 CS 2 加合物的羰基伸缩振动频率来评估配体的电子效应 [21] , 与过渡金属羰基化合物不同的是, 这种加合物上的羧基或二硫代羧基阴离子不会对卡宾空轨道有 π 反馈作用, 故其反映的是配体纯粹的 σ 给电子作用 [22] .…”

Section: Caacsunclassified

“…结果发现 6•CO 2 的伸缩振动频率为 1676 cm -1 [22] , 与之前报道的 IMes•CO 2 加合物(1675 cm -1 ) 类似, 而比 SIMes•CO 2 加合物(1684 cm -1 )稍低 [23] , 即 σ 给电子能力表 1 不同配体给电子能力大小的比较 [8] 2078 1993 2036 5 [8] 2077…”

Section: Caacsunclassified

Cyclic(alkyl)(amino)carbenes and the Research Prospect in Olefin Metathesis Reaction

蔡援¹,

开铖²,

黄毅勇³

et al. 2014

Chin. J. Org. Chem.

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Olefin metathesis has been one of the most important methods to construct carbon-carbon double bonds, which has been enabled by development of well-defined transition-metal catalysts (e.g. [L 2 X 2 Ru＝CHR], L＝PCy 3 ). A significant gain to increase the catalyst stability and activity was achieved after replacing a single PCy 3 ligand of L 2 X 2 Ru＝CHR (L＝PCy 3 ) with cyclic biamino cabene, such as 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene (H 2 IMes). In 2005, Bertrand et al. discovered a novel ligand-yclic(alkyl)(amino)cabene (CAAC), which displayed more electron donating and more electrophilic in comparison with cyclic diamino cabene. It is logic that more electronegative amino group is replaced by alkyl group in CAAC. Furthermore, a quaternary carbon at the α position of carbene center of CAAC may make a big difference from cyclic diamino cabene, which can change the steric environment of CAAC easily and creat a chiral center next to the carbene. In this research prospect, synthesis, property and application of CAACs in olefin metathesis catalysis are introduced. Finally, the issues remained in this research area are summarized and an outlook for the development in the future is given.

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“…It has previously been reported that NHCs with Pr to afford an amidinate, while a bulky cyclic (alkyl)(amino)carbene (CAAC) does not react under these conditions. 9 The steric bulkiness of these carbenes might determine whether the reaction between carbenes and carbodiimides occurs. The steric demand of these carbenes can be quantified by the %V bur values (%V bur : 1a = 49.9; CAAC = 50.7; NHC i Pr ¼ 28:1.…”

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Phosphorylation of Isocyanates and Aldehydes Mediated by Multifunctional N-Phosphine Oxide-substituted Imidazolylidenes

et al. 2017

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The direct syntheses of imidic-phosphinic mixed anhydrides and phosphinates were accomplished via phosphorylation of isocyanates or aldehydes with N-phosphine oxide-substituted imidazolylidenes (PoxIms) that are equipped with both nucleophilic carbene and electrophilic phosphorus moieties. In addition, the catalytic cyclotrimerization of phenyl isocyanate took place by employing a PoxIm having bis-N-phosphine oxide groups. The results presented in the current study demonstrate that judiciously designed multifunctional carbenes represent a promising potential for the phosphorylation of heterocumulenes and carbonyl compounds. Keywords: N-Heterocyclic carbene (NHC) | Phosphine oxide | PhosphorylationOver the past couple of decades, N-heterocyclic carbenes (NHCs) have found a multitude of applications in diverse research areas in organic, inorganic, and organometallic chemistry.1 The advancement of these research areas has largely benefitted from the advent of novel NHCs and other stable carbenes that exhibit unprecedented functionality.2 Among these examples, NHC derivatives containing a phosphorus-based functional group have been extensively employed as multidentate ligands for transition metals.3 However, there are only few reports on NHCs that contain a phosphine oxide moiety. 4,5 The reactivity of these carbenes should be of substantial interest as the phosphine oxide moiety could function as a hemi-labile coordination ligand, 4b,5c as well as an electron-withdrawing substituent. 4a We developed N-phosphine oxide-substituted imidazolylidenes (PoxIms) as a novel type of isolable NHCs, 5a that afforded carboxylic-phosphinic mixed anhydrides via direct phosphorylation of CO 2 (Scheme 1).5b The resulting mixed anhydride was subsequently transformed into a variety of unsymmetrical carbonyl compounds via the corresponding imidazolium salt followed by a sequential double substitution reaction. In this work, we envisioned that the direct syntheses of imidicphosphinic mixed anhydrides and phosphinates could be achieved by the treatment of PoxIms with isocyanates and aldehydes, respectively (Scheme 1). These unprecedented transformations should offer novel and efficient methods for phosphorylation of carbonyl compounds.6 Given the significant utility of these organophosphorus compounds that are frequently encountered in bioactive reagents as well as industrial commodities, 6a6d development of an efficient phosphorylation method should be noteworthy. Herein, we report the phosphorylation of isocyanates and aldehydes by using PoxIms.The reaction of phenyl isocyanate (2a) with PoxIm 1a in toluene at room temperature afforded mixed anhydride 3a in 95% yield through the formation of the oxygenphosphorous bond (Scheme 2), which was unambiguously confirmed by single-crystal X-ray diffraction analysis (Figure 1a). In the 13 C NMR spectrum, the resonances for C1 and C2 are observed at ¤ C 140.4 ( 2 J C,P = 12.0 Hz) and 129.2 ppm ( 3 J C,P = 12.0 Hz), respectively. In the 31 P NMR spectrum, the resonance for the phosphinate ...

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Reactivity of Cyclic (Alkyl)(amino)carbenes (CAACs) and Bis(amino)cyclopropenylidenes (BACs) with Heteroallenes: Comparisons with their N‐Heterocyclic Carbene (NHCs) Counterparts

Cited by 47 publications

References 77 publications

Reactivity of a Stable Phosphinonitrene towards Small Molecules

Reactivity of a Stable Phosphinonitrene towards Small Molecules

Cyclic(alkyl)(amino)carbenes and the Research Prospect in Olefin Metathesis Reaction

Phosphorylation of Isocyanates and Aldehydes Mediated by Multifunctional N-Phosphine Oxide-substituted Imidazolylidenes

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