147609-46-9Relevant academic research and scientific papers
Nickel-Catalysed Allylboration of Aldehydes
Dennis, Francesca M.,Partridge, Benjamin M.,Robertson, Craig C.
, p. 1903 - 1914 (2020/07/04)
A nickel catalyst for the allylboration of aldehydes is reported, facilitating the preparation of homoallylic alcohols in high diastereoselectivity. The observed diastereoselectivities and NMR experiments suggest that allylation occurs through a well-defined six-membered transition state, with nickel acting as a Lewis acid.
Palladium-Catalyzed Oxidative Borylation of Allylic C-H Bonds in Alkenes
Mao, Lujia,Bertermann, Rüdiger,Rachor, Simon G.,Szabó, Kálmán J.,Marder, Todd B.
supporting information, p. 6590 - 6593 (2017/12/26)
This communication describes an efficient palladium pincer complex-catalyzed allylic C-H borylation of alkenes. The transformation exhibits high regio- and stereoselectivity with a variety of linear alkenes. A synthetically useful feature of this allylic C-H borylation method is that all allyl-Bpin products can be isolated in usually high yields. Preliminary mechanistic studies indicate that this C-H borylation reaction proceeds via Pd(IV) pincer complex intermediates.
Direct synthesis of alkenyl boronic esters from unfunctionalized alkenes: A boryl-heck reaction
Reid, William B.,Spillane, Jesse J.,Krause, Sarah B.,Watson, Donald A.
supporting information, p. 5539 - 5542 (2016/05/24)
We report the first example of a boryl-Heck reaction using an electrophilic boron reagent. This palladium-catalyzed process allows for the conversion of terminal alkenes to trans-alkenyl boronic esters using commercially available catecholchloroborane (catBCl). In situ transesterification allows for rapid access to a variety of boronic esters, amides, and other alkenyl boron adducts.
Cross-metathesis/isomerization/allylboration sequence for a diastereoselective synthesis of anti-homoallylic alcohols from allylbenzene derivatives and aldehydes
Hemelaere, Rmy,Carreaux, Franois,Carboni, Bertrand
, p. 14518 - 14523 (2015/01/09)
We describe a highly diastereoselective approach to anti-homoallylic alcohols from allylbenzene derivatives and aldehydes. The strategy is based on a cross-metathesis/isomerization/allylboration sequence catalyzed successively by ruthenium and iridium. This methodology provides another way to access this class of compounds, which leads to the preparation of hitherto-unknown homoallylic alcohols without the requirement to control the stereochemistry of the 1-alkenyl boronate intermediates. Our study towards an enantioselective version of this sequential reaction is also reported.
Highly selective copper-catalyzed hydroboration of allenes and 1,3-dienes
Semba, Kazuhiko,Shinomiya, Masataka,Fujihara, Tetsuaki,Terao, Jun,Tsuji, Yasushi
, p. 7125 - 7132 (2013/07/04)
The highly selective copper-catalyzed hydroboration of allenes has been developed. Allylboranes and alkenylboranes were selectively prepared by the judicious choice of catalytic species (copper hydride and boryl copper). Furthermore, two types of alkenylboranes could be selectively synthesized by the choice of an appropriate ligand. Mechanistic studies confirmed that the protonation of a (Z)-σ-allyl copper species, which was isolated and structurally characterized by single-crystal X-ray diffraction, was a key step in these reactions. Besides allenes, this method is also applicable to the selective hydroboration of 1,3-diene derivatives to afford allylboranes and homoallylboranes. Copyright
Regioselective copper-catalyzed carboxylation of allylboronates with carbon dioxide
Duong, Hung A.,Huleatt, Paul B.,Tan, Qian-Wen,Shuying, Eileen Lau
supporting information, p. 4034 - 4037 (2013/09/02)
In the presence of a Cu(I)/NHC catalyst, the reactions of allylboronic pinacol esters with CO2 (1 atm) are highly regioselective, giving exclusively the more substituted β,γ-unsaturated carboxylic acids in most cases. A diverse array of substituted carboxylic acids can be prepared via this method, including compounds featuring all-carbon quaternary centers.
Ni- and pd-catalyzed synthesis of substituted and functionalized allylic boronates
Zhang, Ping,Roundtree, Ian A.,Morken, James P.
, p. 1416 - 1419 (2012/06/01)
Two highly efficient and convenient methods for the synthesis of functionalized and substituted allylic boronates are described. In one procedure, readily available allylic acetates are converted to allylic boronates catalyzed by Ni/PCy3 or Ni/PPh3 complexes with high levels of stereoselectivity and in good yields. Alternatively, the borylation can be accomplished with commercially available Pd catalysts [e.g., Pd 2(dba)3, PdCl2, Pd/C], starting with easily accessed allylic halides.
Palladium-catalyzed allylic C-OH functionalization for efficient synthesis of functionalized allylsilanes
Selander, Nicklas,Paasch, Jennifer R.,Szabo, Kalman J.
supporting information; experimental part, p. 409 - 411 (2011/04/15)
A new method is described for palladium-catalyzed allylic silylation using allylic alcohols and disilanes as precursors. The reactions proceed smoothly under mild and neutral conditions, and this method is suitable for synthesis of regioand stereodefined allylsilanes. The presented silylation reaction can be easily extended to include synthesis of allylboronates by change of the dimetallic reagent. The presented synthetic procedure offers a broad platform for the selective synthesis of functionalized allyl metal reagents, which are useful precursors in advanced organic chemistry and natural product synthesis.
Electrochemical preparation of pinacol allylboronic esters
Godeau, Julien,Pintaric, Christine,Olivero, Sandra,Du?ach, Elisabet
, p. 5116 - 5119 (2009/07/10)
The electroreduction of allylic halide derivatives in the presence of pinacolborane afforded allylboronic pinacol esters with moderate to good yields (up to 86%) and high regioselectivities. The electrosynthesis was carried out in a single-compartment cel
Performance of SCS palladium pincer complexes in borylation of allylic alcohols. Control of the regioselectivity in the one-pot borylation-allylation process
Selander, Nicklas,Szabo, Kalman J.
supporting information; experimental part, p. 5695 - 5698 (2009/12/06)
(Chemical Equation Presented) One-pot borylation-allylation reactions of aldehydes and allylic alcohols were performed under various reaction conditions. The borylation of allylic alcohols was performed using a very efficient SCS palladium pincer-complex catalyst. The regioselectivity of the allylation depends on the applied solvent. The reaction in CHCl3 gave the linear allylic product; however, when MeOH was added to the reaction mixture, the branched allylic product was formed.
