Simple Route to Adducts of (Amino)(aryl)carbene with Phosphorus Pentafluoride
作者:Olexandr I. Guzyr、Sergiy V. Zasukha、Yurii G. Vlasenko、Alexander N. Chernega、Alexander B. Rozhenko、Yuriy G. Shermolovich
DOI:10.1002/ejic.201300563
日期:2013.8.12
The tetramethyl ester of (hydroxy)(phenyl)methylenebis(phosphonic acid) reacts with morpholinosulfur trifluoride (MOST) to provide, along with the expected product of the substitution of a hydroxy group by fluorine, the adduct of (morpholino)(phenyl)carbene with PF5, compound 3a. Fluorination of dimethyl α-aroylphosphonates with MOST yields adducts of (amino)(aryl)carbene with PF5 (p-XC6H4)(Morph)C:PF5
(羟基)(苯基)亚甲基双(膦酸)的四甲酯与吗啉代三氟化硫(MOST)反应,与氟取代羟基的预期产物一起提供(吗啉代)(苯基)卡宾的加合物与PF5,化合物3a。用 MOST 氟化 α-芳酰基膦酸二甲酯生成(氨基)(芳基)卡宾与 PF5 (p-XC6H4)(Morph)C:PF5 [3a–f,其中 Morph 是吗啉,X = H (a),Me ( b)、OEt(c)、F(d)、Cl(e)、CF3(f)]作为主要反应产物。提出的反应机理是基于实验数据和 DFT 计算。加合物 3a 的结构由 X 射线研究确定。分别在苯环上带有取代基 Cl 和 CF3 的化合物 3e 和 3f 水解,产生以前未知的苯甲酰五氟磷酸盐 [p-XC6H4–C(=O)PF5]–MorphH+。
Studies on Organophosphorus Compounds, 53: A New Procedure for the Synthesis of 1-Alkyl or 1-Aryl-1-hydroxy-2-nitroethylphoshonates under PTC Conditions
A series of dialkyl 1-alkyl- or 1-aryl-1-hydroxy-2-nitroethyl-phosphonates and 1-hydroxy-1-(nitromethyl)alkylphosphonates was prepared by nucleophilic addition of nitromethane to dialkyl acylphosphonates in the presence of potassium carbonate and tetrabutylammonium bromide.
Organocatalytic Highly Enantioselective Nitroaldol Reaction of α-Ketophosphonates and Nitromethane
作者:Tanmay Mandal、Sampak Samanta、Cong-Gui Zhao
DOI:10.1021/ol070209i
日期:2007.3.1
[reaction: see text] The first organocatalytichighlyenantioselective nitroaldol reaction of alpha-ketophosphonates and nitromethane has been realized by using cupreine (2) or 9-O-benzylcupreine (3) as the catalyst. Both catalysts are highly reactive and highlyenantioselective. alpha-Hydroxy-beta-nitrophosphonates have been synthesized in good yields and excellent enantioselectivities (>or=90% ee) at a low
Enantio- and Diastereoselective Vinylogous Mukaiyama Aldol Reactions of α-Keto Phosphonates with 2-(Trimethylsilyloxy)- furan Catalyzed by Bis(oxazoline)-Copper Complexes
The asymmetric vinylogousMukaiyamaaldolreaction between α-keto phosphonate and 2-(trimethylsilyloxy)furan was performed by using bis(oxazoline)-copper complexes as the catalyst and 2,2,2-trifluoroethanol as additive in dichloromethane. The present method is highly tolerable for functionalized α-keto phosphonates and enabled us to obtain the corresponding 3- and 4-substituted benzyl-functionalized
The aldol reactions of α-keto phosphonates and aldehydes were facilitated by an axially chiral biphenylprolinamide under mild conditions, affording the synthetically and pharmaceutically useful products in high yields and excellent enantioselectivities.