98061-48-4Relevant academic research and scientific papers
Petasis borono-Mannich reaction and allylation of carbonyl compounds via transient allyl boronates generated by palladium-catalyzed substitution of allyl alcohols. An efficient one-pot route to stereodefined α-amino acids and homoallyl alcohols
Selander, Nicklas,Kipke, Andreas,Sebelius, Sara,Szabo, Kalman J.
, p. 13723 - 13731 (2007)
An efficient one-pot procedure was designed by integration of the pincer-complex-catalyzed borylation of allyl alcohols in the Petasis borono-Mannich reaction and in allylation of aldehydes and ketones. These procedures are suitable for one-pot synthesis of α-amino acids and homoallyl alcohols from easily available allyl alcohol, amine, aldehyde, or ketone substrates. In the presented transformations, the active allylating agents are in situ generated allyl boronic acid derivatives. These transient intermediates are proved to be reasonably acid-, base-, alcohol-, water-, and air-stable species, which allows a high level of compatibility with the reaction conditions of the allylation of various aldehyde/ketone and imine electrophiles. The boronate source of the reaction is diboronic acid or in situ hydrolyzed diboronate ester ensuring that the waste product of the reaction is nontoxic boric acid. The regio- and stereoselectivity of the reaction is excellent, as almost all products form as single regio- and stereoisomers. The described procedure is suitable to create quaternary carbon centers in branched allylic products without formation of the corresponding linear allylic isomers. Furthermore, products comprising three stereocenters were formed as single products without formation of other diastereomers. Because of the highly disciplined consecutive processes, up to four-step, four-component transformations could be performed selectively as a one-pot sequence. For example, stereodefined pyroglutamic acid could be prepared from a simple allyl alcohol, a commercially available amine, and glyoxylic acid in a one-step procedure. The presented method also grants an easy access to stereodefined 1,7-dienes that are useful substrates for Grubbs ring-closing metathesis.
Mechanistic Studies of the TRIP-Catalyzed Allylation with Organozinc Reagents
Hartmann, Peter E.,Lazzarotto, Mattia,Pletz, Jakob,Tanda, Stefan,Neu, Philipp,Goessler, Walter,Kroutil, Wolfgang,Boese, A. Daniel,Fuchs, Michael
, p. 9672 - 9679 (2020/09/03)
3,3-Bis(2,4,6-triisopropylphenyl)-1,1-binaphthyl-2,2-diyl hydrogenphosphate (TRIP) catalyzes the asymmetric allylation of aldehydes with organozinc compounds, leading to highly valuable structural motifs, like precursors to lignan natural products. Our previously reported mechanistic proposal relies on two reaction intermediates and requires further investigation to really understand the mode of action and the origins of stereoselectivity. Detailed ab initio calculations, supported by experimental data, render a substantially different mode of action to the allyl boronate congener. Instead of a Br?nsted acid-based catalytic activation, the chiral phosphate acts as a counterion for the Lewis acidic zinc ion, which provides the activation of the aldehyde.
Catalytic, nucleophilic allylation of aldehydes with 2-substituted allylic acetates: Carbon-carbon bond formation driven by the water-gas shift reaction
Denmark, Scott E.,Matesich, Zachery D.
, p. 5970 - 5986 (2014/07/21)
The ruthenium-catalyzed allylation of aldehydes with allylic acetates has been expanded to incorporate substituents at the 2-position of the allylic components. Allylic acetates bearing a variety of substituents (CO 2-t-Bu, COMe, Ph, CH(OEt)su
One-pot sequential deoximation and allylation reactions of aldoximes in aqueous solution
Lin, Mei-Huey,Lin, Long-Zhi,Chuang, Tsung-Hsun,Liu, Han-Jun
experimental part, p. 2630 - 2635 (2012/04/23)
A simple procedure has been developed for conducting tin-mediated deoximation and allylation reactions of aldoximes in water to form homoallylic alcohols. Employing the new conditions, various homoallylic alcohols were produced in good to excellent yields
Synthesis of (E)- and (Z)-α-alkylidene-γ-aryl-γ- butyrolactones via alkenylalumination of oxiranes
Ramachandran, P. Veeraraghavan,Garner, Garrett,Pratihar, Debarshi
, p. 4753 - 4756 (2008/03/14)
(Chemical Equation Presented) Alkenylalumination of substituted styrene oxides with [α-(ethoxycarbonyl)alkenyl]diisobutylaluminum, in the presence of BF3·Et2O, affords the corresponding (Z)-α-alkylidene-γ-aryl-γ-hydroxy esters in 81-
Highly selective and robust palladium-catalyzed carbon-carbon coupling between allyl alcohols and aldehydes via transient allylboronic acids
Selander, Nicklas,Sebelius, Sara,Estay, Cesar,Szabo, Kalman J.
, p. 4085 - 4087 (2007/10/03)
The highly regio- and stereoselective coupling of allyl alcohols with aldehydes could be achieved with 5 mol-% of SeCSe pincer complex catalyst and p-toluenesulfonic acid in the presence of diboronic acid. The transformations have a broad synthetic scope, and the high yields were obtained without the use of an inert atmosphere and carefully dried solvents. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
Preparation of allyltin reagents grafted on solid support: Clean and easily recyclable reagents for allylation of aldehydes
Chretien, Jean-Mathieu,Zammattio, Francoise,Gauthier, Delphine,Le Grognec, Erwan,Paris, Michael,Quintard, Jean-Paul
, p. 6816 - 6828 (2007/10/03)
The preparation of polymer-supported allyltin reagents was shown to be possible for both unfunctionalized and functionalized allyl units. These reagents were treated with aldehydes in the presence of cerium(III) or indium(III) salts to afford high yields
Lead-promoted 2-carboethoxyallylation or 2-carboxylallylation of aldehydes: A new and facile method for the synthesis of α-methylene-γ-butyroactones
Zhou,Jia,Yao,Wu
, p. 2397 - 2406 (2007/10/03)
In the presence of powdered lead, the reaction of aldehydes and α-bromomethylacrylate (or α-bromomethylacrylic acid) can be carried out under mild condition, the products 4-hydroxy-2-methylenebutanoates (or 4-hydroxy-2-methylenebutanoic acids) can be easi
A SIMPLE AND GENERAL APPROACH FOR THE SYNTHESIS OF 2-SUBSTITUTED 4-ETHOXYCARBONYLFURAN
Anand, Ramesh C.,Singh, Vibha
, p. 1333 - 1336 (2007/10/02)
A four step strategy has been devised to synthesize 2-substituted 4-ethoxycarbonylfuran starting from an aldehyde.
A new approach for the synthesis of α-methylene-γ-butyrolactones from α-bromomethylacrylic acids (or esters)
Zhou,Lu,Wu
, p. 481 - 487 (2007/10/02)
This paper reports that a new approach for the synthesis of α-methylene-γ-butyrolactones from the reaction of α-bromomethyl acrylic acid (or ester), powdered tin and carbonyl compounds in one pot with excellent to good yields.
