二碘化钐在有机合成中的应用研究

综述了1998年以来二碘化钐在有机合成中的应用研究，主要涉及羰基化合物、 不饱和烃、卤代物、腈及含氧族元素化合物的特殊反应．     

钐试剂在有机合成中应用的若干新进展

综述了本课题组最近几年关于钐试剂在有机合成中应用的研究进展. 主要包括以下几部分内容: (1) 二碘化钐促进的有机反应研究; (2) 金属钐直接应用于有机合成的研究; (3) 其它钐试剂 (三碘化钐, 烯丙基溴化钐) 促进的有机反应研究.     

有机转化中二碘化钐及其他钐试剂近期发展研究

钐试剂自被发现以来,一直在有机合成中占据着一席之地.SmI2优异的单电子转移能力和还原能力都具有重要的研究价值.Sm、allylSmBr、SmI3等其他钐试剂的潜力也逐渐被开发出来.综述了近5年来SmI2以及其他钐试剂介入的反应.主要分为三大部分:(1)SmI2促进的偶联反应研究,(2)其他钐试剂(Sm,allylSm...     

钐试剂在有机合成中的应用

钐试剂在有机合成中的应用是近年来有机合成方法学研究中的热点之一。综述了十余年来本课题组在钐试剂应用于有机合成方面所开展的有关工作：(1)二碘化钐作为偶联剂和还原剂在有机合成中的应用;(2)金属钐直接应用于有机合成;(3)三碘化钐作为路易斯酸应用于有机合成;(4)有机钐试剂在有机合成中的应用。     

二碘化钐还原硫代碳酸酯

在ＳｍＩ＿２－ＨＭＰＡ－ＴＨＦ－ｔ－ＢｕＯＨ体系中，硫代碳酸酯的酰硫键发生还原断裂反应，得到相应的二硫醚产物。     

二碘化钐催化合成1,5-苯并二氮杂草

Samarium diiodide （SmI2） was found to be an efficient catalyst for the condensation of o-phenylenediamine and ketones to afford the corresponding 2,3-dihydro-1H-benzo[b][1,4]-diazepines in moderate to excellent yields under very mild and solvent-free conditions. The real active species here was suggested to be a Sin（Ⅲ） intermediate formed in situ and the mechanism of the present reaction was proposed.     

二碘化钐作用下缺电子烯烃的还原偶联反应

室温下SmI2-HMPA-t-BuOH-THF体系能顺利地将丁烯二酸二酯还原偶联为1, 2, 3, 4-四烷氧基羰基丁烷, 同样条件下, 亚苄基氰乙酸乙酯,α-乙氧羰基肉桂酸乙酯, α-乙酰基肉桂酸乙酯和亚苄基丙二酸亚异丙酯等化合物也发生还原偶联反应得到相应的二聚体。     

钐试剂在有机合成中的应用

本文综述了钐试剂在有机合成中的应用,包括还原反应,碳-碳键形成反应以及催化作用。     

二碘化钐作为预催化剂的有机反应

二碘化钐是二价稀土试剂中的代表化合物,在有机合成中用途广泛.综述了近年来催化量二碘化钐促进的有机反应,介绍了二碘化钐作为预催化剂在催化有机反应方面所体现的反应活性及选择性.     

二碘化钐有效催化芳胺成胍反应的研究

二碘化钐作为易得的路易斯酸型预催化剂,可有效催化芳胺和碳二亚胺的反应,在温和条件下以高收率得到一系列胍。     

Reduction of Elemental Selenium by Samarium Diiodide: the Synthesis of Dithiodiselenides and Dithioselenides

Selenium is an essential element in living organism. It is reported that the selenosulfides have been transported in vivo in glutathione or coenzyme-A1. It is also discovered in low concentration in garlic2. In organic synthesis, selenosulfides are useful intermediates3. Several methods for the formation of sulfur-selenium bond have been reported. For example, the compounds including S-Se bond were prepared by chloroamination of thiols and selenols4; by heating the selenocyanate with thiols5…     

Synthesis of Aminomethyl Arylsulfides via Novel Synthetic Auxiliary Benzotriazole Promoted by Samarium Diiodide

Benzotriazolemethodologyhasalreadycomealongway,butinthelastdecadebenzotriazoleisanexcellentsyntheticauxiliaryinmanyusefulsynthetictransformationsl-5.Becausebenzotriazolateanionisagoodleavinggroup,itmaybeusedinplaceofahalogeninmanyreactions.Theuseofbenzotriazoleasasyntheticauxiliaryhasanumberofsignificantadvantages.Forexample,itisreadilyavailableandquitecheap;itisacidicwithapKaofabout8,whichenableseasyseparationandrecovery.Manytypesofcompoundshavebeensynthesizedviabenzotriazoleauxifiary>.Samar…     

Samarium Diiodide Mediated Reactions in Total Synthesis

Introduced by Henri Kagan more than three decades ago, samarium diiodide (SmI₂) has found increasing application in chemical synthesis. This single‐electron reducing agent has been particularly useful in C? C bond formations, including those found in total synthesis endeavors. This Review highlights selected applications of SmI₂ in total synthesis, with special emphasis on novel transformations and mechanistic considerations. The examples discussed are both illustrative of the power of this reagent in the construction of complex molecules and inspirational for the design of synthetic strategies toward such targets, both natural and designed.     

Synthesis of Polycyclic Tertiary Carbinamines by Samarium Diiodide Mediated Cyclizations of Indolyl Sulfinyl Imines

Samarium diiodide mediated cyclizations of N‐acylated indole derivatives bearing sulfinyl imine moieties afforded polycyclic tertiary carbinamines with moderate to excellent diastereoselectivities. Lithium bromide and water turned out to be the best additives to achieve these transformations in good yields. Using enantiopure sulfinyl imines the outcome strongly depends on the reactivity of the indole moiety. Whereas with unactivated indole derivatives desulfinylation and formation of racemic products was observed, indoles bearing electron‐withdrawing substituents at C‐3 afforded the polycyclic products with intact N‐sulfinyl groups and with excellent diastereoselectivity, finally allowing the preparation of enantiopure tertiary carbinamines. The mechanisms of these processes are discussed.     

Beyond Samarium Diiodide: Vistas in Reductive Chemistry Mediated by Lanthanides(II)

Reactions proceeding through open-shell, single-electron pathways offer attractive alternative outcomes to those proceeding through closed-shell, two-electron mechanisms. In this context, samarium diiodide (SmI(2) ) has emerged as one of the most important and convenient-to-use electron-transfer reagents available in the laboratory. Recently, significant progress has been made in the reductive chemistry of other divalent lanthanides which for many years had been considered too reactive to be of value to synthetic chemists. Herein, we illustrate how new samarium(II) complexes and nonclassical lanthanide(II) reagents are changing the landscape of modern reductive chemistry.