Ionic liquid-mediated benzoyl transfer-coupling in the Suzuki and Sonogashira reactions and aryl transfer-coupling by decarbonylative Heck reaction, using N-Benzoyl-saccharin (NBSac) as reagent
作者:Shruti S. Malunavar、Suraj M. Sutar、Pavankumar Prabhala、Rajesh G. Kalkhambkar、Kenneth K. Laali
DOI:10.1016/j.tetlet.2020.151987
日期:2020.6
of N-benzoyl-saccharin (NBSac) as reagent for selective benzoyl transfer-coupling in the Suzuki reaction in BMIM-IL/[PAIM][NTf2] as solvent/base, and in the Sonogashira reaction employing guanidinium-IL (GIL) as solvent, are demonstrated. Decarbonylative aryl transfer-coupling occurs in the Heck reaction employing GIL as solvent. The reactions are catalyzed by Pd(OAc)2 or NiCl2(dppp), are performed
[Cp*Ir(PPh3)Cl2] with various internal acylalkynes in the presence of NaBArF 4 resulted in the selective formation of iridacycles via vinylidene rearrangement. 13C-labeling experiments revealed that the acyl group selectively migrates to the other acetylenic carbon atom. This trend is the same as that in the vinylidene rearrangement of internal alkynes at a group 8 metal center.
Synthesis of 1-Substituted Cyclopropylamines via Formal Tertiary C<sub>sp<sup>3</sup></sub>–H Amination of Cyclopropanes
作者:Kui Liu、Shao-Jie Cheng、Gen Luo、Zhi-Shi Ye
DOI:10.1021/acs.orglett.1c03687
日期:2021.12.3
A novel and facile approach to synthesis of 1-substituted cyclopropylamines via phosphine-catalyzed formal tertiary Csp3–H amination of cyclopropanes was described. The indoles, pyrroles, imidazoles, uracils, 2-pyridone, pyrimidin-4(3H)-one, and phthalimide had been proven as good aminating partners. The present protocol features transition-metal-free, excellent regioselectivity, high-atom-economy
描述了一种通过膦催化环丙烷的形式叔 C sp 3 -H 胺化合成 1-取代环丙胺的新方法。吲哚类、吡咯类、咪唑类、尿嘧啶类、2-吡啶酮、pyrimidin-4(3 H)-one,邻苯二甲酰亚胺已被证明是良好的胺化伙伴。本协议具有无过渡金属、优异的区域选择性、高原子经济性、温和的反应条件和广泛的底物。该协议的实用性还可以通过生物活性分子的后期修饰、放大反应和发散衍生化来证明。值得注意的是,该方法已用于激素敏感性脂肪酶 (HSL) 抑制剂的正式合成。通过实验和计算研究阐明了机械方面。
Acid-promoted cleavage of the C–C double bond of N-(2-Hydroxylphenyl)enaminones for the synthesis of benzoxazoles
An acid-mediated selective cleavage of C–C doublebond of N-(2-hydroxylphenyl)enaminones with formation a new C–O bond for the synthesis of 2-substituted benzoxazoles has been developed. This protocol proceeds under transition metal- and oxidant-free conditions with broad functional group tolerance. The oxidative cleavage of C–C doublebond of N-(2-hydroxylphenyl)enaminone is also realized using NCS
<scp>Palladium‐Catalyzed</scp>
Oxidative C≡C Triple Bond Cleavage of
<scp>2‐Alkynyl</scp>
Carbonyl Compounds Toward 1,
<scp>2‐Dicarbonyl</scp>
Compounds
<sup>†</sup>
作者:Ming‐Bo Zhou、Mu‐Jia Luo、Ming Hu、Jin‐Heng Li
DOI:10.1002/cjoc.202000040
日期:2020.6
palladium‐catalyzed oxidative strategy for the cleavage of the C≡C triple bond is presented. By employing PdCl2, CuBr2, TEMPO and air as the catalytic system and H2O as the carbonyl oxygen atom source, a wide range of 2‐alkynyl carbonylcompounds, including 1,3‐disubstituted prop‐2‐yn‐1‐ones, propiolamides and propiolates, lost an alkynyl carbon to access various 1,2‐dicarbonyl compounds, e.g., 1,2‐diones