39551-05-8Relevant articles and documents
Active bismuth mediated allylation of carbonyls/N-tosyl aldimines and propargylation of aldehydes in water
Sawkmie, Micky Lanster,Paul, Dipankar,Khatua, Snehadrinarayan,Chatterjee, Paresh Nath
, (2019/06/08)
Abstract: Active bismuth is synthesized by the chemical reduction of bismuth trichloride using freshly prepared sodium stannite solution as the reducing agent at room temperature. The as-synthesized active bismuth is applied as a reagent for the synthesis of homoallyl alcohol/homopropargyl alcohol from allyl bromide/propargyl bromide and carbonyl compounds in water at 50°C. The homoallyl amines are also synthesized from N-tosyl aldimines and allyl bromide using active bismuth reagent in good yields. No assistance of organic co-solvent, co-reagent, phase transfer catalyst or inert atmosphere is required for this reaction. The waste bismuth material obtained after the completion of the organic reaction can be reduced to active bismuth by sodium stannite solution and successfully reused for mediating the allylation of aldehydes. Graphical Abstract:: Synopsis Active bismuth mediated allylation/crotylation of aldehydes is developed in water to get homoallyl alcohols. The method is also applied for the allylation of N-tosyl aldimines and propargylation of aldehydes in water to achieve the homoallyl amines and homopropargyl alcohols, respectively. The reactions do not require the assistance of organic co-solvent, co-reagent, phase transfer catalyst or inert atmosphere.[Figure not available: see fulltext.].
Interruption of Formal Schmidt Rearrangement/Hosomi-Sakurai Reaction of Vinyl Azides with Allyl/Propargylsilanes
Fang, Guichun,Liu, Zhenhua,Cao, Shanshan,Yuan, Haiyan,Zhang, Jingping,Pan, Ling
, p. 7113 - 7116 (2018/11/23)
An interrupted Schmidt rearrangement/Hosomi-Sakurai reaction of N-tosyl and S-substituted vinyl azides is reported. With BF3·Et2O as a Lewis acid promoter, the denitrogenative fragmentation of vinyl azides facilitates the generation of the N/S-stabilized carbocations, which further undergo nucleophilic addition by allyl/propargylsilanes for C-C bond formation. As a result, a variety of homoallylic/allenylic amines can be afforded in good yields under mild reaction conditions with well-defined functional-group tolerance.
Assembly of homoallylamine derivatives through iron-catalyzed three-component sulfonamidoallylation reaction
Fan, Xiaohui,Zhu, Hong-Bo,Lv, Hao,Guo, Kun,Guan, Yong-Hong,Cui, Xiao-Meng,An, Bin,Pu, Yan-Ling
, p. 588 - 592 (2015/09/01)
An efficient FeCl3-catalyzed three-component reaction between aldehydes, sulfonamides and allylsilanes has been achieved, which provides a convenient, atom-economic and green way to construct homoallylamine derivatives. In addition, this reaction exhibits excellent syn stereoselectivity with γ-substituted allylsilanes. A practical three-component cascade process to homoallylamine derivatives is reported, which uses cheap and environmentally benign FeCl3 as catalyst and shows excellent syn stereoselectivity with γ-substituted allylsilanes.
Pd-containing organopolyoxometalates derived from Dawson polyoxometalate [P2W15V3O62]9-: Lewis acidity and dual site catalysis
Riflade, Benoit,Lachkar, David,Oble, Julie,Li, Joaquim,Thorimbert, Serge,Hasenknopf, Bernold,Lacote, Emmanuel
supporting information, p. 3860 - 3863 (2014/08/18)
Grafting of a palladium complex to the Dawson vanadotungstate polyanion [P2W15V3O62]9- via an organic ligand generates a large family of pincer-type hybrid polyoxometalates. The palladium-POM derivatives have dual catalytic properties. Unlike their parent inorganic polyanions, they catalyze allylations while retaining their oxidant character, which leads to single-pot dual site catalysis. This opens a new route for multicatalytic reactions.
Iron-catalyzed N-alkylation using π-activated ethers as electrophiles
Fan, Xiaohui,Fu, Lin-An,Li, Na,Lv, Hao,Cui, Xiao-Meng,Qi, Yuan
, p. 2147 - 2153 (2013/04/10)
A new method for the synthesis of diverse N-alkylation compounds was developed via an iron-catalyzed etheric Csp3-O cleavage with the C-N bond formation in the reaction of π-activated ethers with various nitrogen-based nucleophiles. In addition, the mechanism of this reaction was investigated. The Royal Society of Chemistry 2013.
Influence of the ligand backbone in pincer complexes: Indenediide-, indolyl-, and indenyl-based SCS palladium complexes
Lisena, Jeroime,Monot, Julien,Mallet-Ladeira, Sonia,Martin-Vaca, Blanca,Bourissou, Didier
supporting information, p. 4301 - 4305 (2013/09/02)
A new pincer ligand featuring an indolyl backbone was prepared and coordinated to palladium. The properties of related indenediide-, indenyl-, and indolyl-based complexes have been compared by spectroscopic and structural means. Modulation of the ligand backbone was shown to significantly influence the electron density at Pd. Its impact on catalytic performance has been illustrated in the Pd-catalyzed imine allylation. The higher the electron density at Pd, the more active the SCS pincer complex.
Enantioselective rhodium-catalyzed nucleophilic allylation of cyclic imines with allylboron reagents
Luo, Yunfei,Hepburn, Hamish B.,Chotsaeng, Nawasit,Lam, Hon Wai
scheme or table, p. 8309 - 8313 (2012/09/07)
Chiral allylrhodium nucleophiles: The highly diastereo- and enantioselective title reaction of a range of cyclic imines with various potassium allyltrifluoroborates most likely proceeds via allylrhodium(I) intermediates, and represents the first rhodium-catalyzed enantioselective nucleophilic allylation of π electrophiles with allylboron compounds. Copyright
Synthesis of 2-amino-1,3-dienes by chromium-catalyzed addition of silylated propargyl bromides to imines
Durán-Galván, María,Connell, Brian T.
experimental part, p. 7901 - 7908 (2011/11/07)
(Silyl)methylallenic amines were synthesized by the chromium-catalyzed addition of (4-bromobutynyl)trimethylsilane to tosyl imines. Regioisomeric mixtures of the desired allene and the corresponding alkyne were obtained. Allenic imines were then treated w
Lewis acid-catalyzed oxidative allylation: A new approach for the synthesis of homoallylic alcohols and amines directly from alcohols
Srivastava, Vishnu P.,Patel, Rajesh,Yadav, Lal Dhar S.
supporting information; experimental part, p. 695 - 700 (2011/05/06)
A new approach for the synthesis of homoallylic alcohols and amines directly from alcohols via one-pot sequential oxidation-Barbier reaction and oxidation-condensation-Barbier reactions, respectively, is reported. The protocol involves the one-pot ferric chloride-catalyzed oxidation of alcohols to the corresponding aldehydes with chloramine-T followed by indium-mediated Barbier allylation with allyl bromide to afford homoallylic alcohols in 70-90% overall yields. The ferric chloride-catalyzed condensation of aldehydes and oxidation by-product p-toluenesulfonamide followed by indium-mediated Barbier-type allylation of the resulting aldimines with allyl bromide affords homoallylic amines in 60-80% overall yields in the same reaction vessel. The present work demonstrates a new one-pot approach toward homoallylic alcohol and amine synthesis directly from alcohols. Copyright
Chiral amino alcohol derived bis-phosphoramidite pincer palladium complexes and their applications in asymmetric allylation of aldimines
Li, Jie,Lutz, Martin,Spek, Anthony L.,Van Klink, Gerard P. M.,Van Koten, Gerard,Klein Gebbink, Robertas J. M.
experimental part, p. 1379 - 1387 (2010/05/15)
Novel P-stereogenic bis-phosphoramidite pincer palladium complexes 1 and 2 derived from (S)-(-)-α,α-diphenyl-2-pyrrolidinemethanol and (S)-(+)-indolinemethanol, respectively, were synthesized in reasonable yields (i.e., 55-62%) by using a flexible, modular synthetic approach and were characterized by X-ray crystal structure determination. Reacting (S)-(+)-indolinemethanol with PCl3 leads to the formation of a novel P-chiral building block, which exhibits good thermal stability of its stereochemical features. This enabled the design and development of new P-chiral bisphosphoramidite pincer arene ligands and their corresponding metal complexes. The molecular structure of the new indolinemethanol-derived phosphoramidite pincer metal complex screens quadrants I and III, which is in contrast to the previously reported L-proline-derived P-chiral ligands that screen quadrants II and IV. The bis-phosphoramidite pincer palladium, complexes 1 and 2 are active catalysts for asymmetric homoallylation of sulfonimines, where low (ee 33%) or no enantioselectivity was observed for reactions catalyzed by 2 and 1, respectively. Preliminary catalytic results revealed that enantiomeric excess values varied by using differently functionalized sulfonimines, suggesting that, both electronic properties and steric congestion of sulfonimines affect, the transition state of the electrophilic attack of the 1nallyl Pd intermediate in the allylation.
