73178-44-6Relevant academic research and scientific papers
Rhodium-Catalyzed Alkenylation of Toluene Using 1-Pentene: Regioselectivity to Generate Precursors for Bicyclic Compounds
Liebov, Nichole S.,Zhu, Weihao,Chen, Junqi,Webster-Gardiner, Michael S.,Schinski, William L.,Gunnoe, T. Brent
supporting information, p. 3844 - 3851 (2019/10/16)
Rhodium catalysts for arene alkenylation reported by our group (e.g., Science 2015, 348, 421; J. Am. Chem. Soc. 2017, 139, 5474; J. Am. Chem. Soc. 2018, 140, 17007) have demonstrated selectivity for 1-aryl alkenes over y-aryl alkenes (y > 1). This selectivity is notable because 1-aryl alkenes or 1-aryl alkanes cannot be generated using acid-based Friedel-Crafts arene alkylation or acidic zeolite catalysts. Herein, we report the extension of Rh arene alkenylation catalysis to generate 1-tolyl-1-pentenes, which are potential precursors for bicyclic compounds. The olefin concentration, copper(II) oxidant identity and concentration, reaction temperature, and rhodium concentration for the alkenylation of toluene with 1-pentene have been optimized using [Rh(Η2-C2H4)2(μ-OAc)]2 as the catalyst precursor. The rhodium-based catalysis achieves up to 12(1):1 anti-Markovnikov selectivity for 1-tolyl-1-pentenes over 2-tolyl-2-pentenes and is selective for alkenylation in the meta and para positions.
Direct transformation of aryl 2-pyridyl esters to secondary benzylic alcohols by nickel relay catalysis
Wu, Xianqing,Li, Xiaobin,Huang, Wenyi,Wang, Yun,Xu, Hui,Cai, Liangzhen,Qu, Jingping,Chen, Yifeng
supporting information, p. 2453 - 2458 (2019/03/29)
A direct transformation of aryl esters to secondary benzylic alcohols via tandem Ni-catalyzed cross-coupling reactions of aromatic 2-pyridyl esters with alkyl zinc reagents and carbonyl group reduction by Ni-H species is achieved. Preliminary mechanistic studies reveal that the Ni-H species is generated in situ via β-hydride elimination of the Negishi reagents. The reaction is catalyzed by bench-stable nickel salts under mild conditions with wide functional group tolerance.
Probing solvent effects on mixed aggregates associating a chiral lithium amide and n-BuLi by NMR: From structure to reactivity
Barozzino-Consiglio, Gabriella,Rouen, Mathieu,Oulyadi, Hassan,Harrison-Marchand, Anne,Maddaluno, Jacques
, p. 14219 - 14228 (2014/12/11)
An NMR study of a 1 : 1 mixture of a chiral lithium amide (4a) and n-BuLi shows that depending on the solvent employed (Et2O or THF) a mixed aggregate can form in proportions that are directly related to the ees measured during the enantioselec
Anion relay chemistry: Access to the type II ARC reaction manifold through a fundamentally different reaction pathway exploiting 1-oxa-2-silacyclopentanes and related congeners
Smith III, Amos B.,Tong, Rongbiao,Kim, Won-Suk,Maio, William A.
, p. 8904 - 8907 (2011/10/19)
Distinctly different: Two 1-oxa-2-silacyclopentenes and a saturated congener have been synthesized and demonstrated to provide access to type II anion relay chemistry (ARC) through a fundamentally new mechanistic pathway. Similar to previous studies, but contrary to initial hypothesis, Brook rearrangement additives (hexamethylphosphoramide and CuI) are necessary to promote Si migration and anion capture.
A novel one-pot synthesis of secondary alcohols from esters
Chae, Min Jung,Jeon, Ah Ram,Park, Jae Kyo,An, Duk Keun
experimental part, p. 1718 - 1720 (2011/04/25)
Alkylation or vinylation by using organometallic reagents after partial reduction of carboxylic esters with LDBBA gave secondary alcohols, also involving allyl alcohols, without any isolation of intermediates in good yield (54-78%).
Nickel-catalyzed alkylation of aldehydes with trialkylboranes
Hirano, Koji,Yorimitsu, Hideki,Oshima, Koichiro
, p. 4689 - 4691 (2007/10/03)
(Chemical Equation Presented) Nickel-catalyzed alkylation of aldehydes with trialkylboranes proceeds smoothly in the presence of a catalytic amount of 5-allyl-1,2,3,4,5-pentamethyl-1,3-cyclopentadiene or an excess of cesium carbonate to afford the corresponding secondary alcohols.
Chiral lithium amido sulfide ligands for asymmetric addition reactions of alkyllithium reagents to aldehydes
Granander, Johan,Sott, Richard,Hilmersson, Goeran
, p. 439 - 447 (2007/10/03)
Six chiral amino sulfides have been synthesised from the amino acids phenylalanine, phenylglycine and valine. These amino sulfides were used as chiral ligands in the asymmetric addition of n-butyllithium and metyllithium to various aldehydes at low temperatures. The highest stereoselectivities were obtained with benzaldehyde, resulting in 1-phenyl-1-pentanol and 1-phenyl-1-ethanol in enantiomeric excesses of >98.5 and 95%, respectively. These stereoselectivities were significantly higher than those induced by the ether analogues.
Structure-selectivity relationship in alkyllithium-aldehyde condensations using 3-aminopyrrolidine lithium amides as chiral auxiliaries
Corruble, Aline,Valnot, Jean-Yves,Maddaluno, Jacques,Duhamel, Pierre
, p. 8266 - 8275 (2007/10/03)
A nonracemizing route to a set of chiral 3-aminopyrrolidines, based on 4-hydroxy-(L)-proline, is described. The induction potential of the lithium amides derived from these diamines has then been investigated in the asymmetric addition of alkyllithium com
Electron-transfer-induced reductive cleavage of phthalans: Reactivity and synthetic applications
Azzena, Ugo,Demartis, Salvatore,Melloni, Giovanni
, p. 4913 - 4919 (2007/10/03)
The behavior of phthalan (1a) was investigated under conditions of electron transfer from alkali metals in aprotic solvents. Reaction with lithium in the presence of a catalytic amount of naphthalene in THF led to the reductive cleavage of an arylmethyl carbon-oxygen bond, with formation of a stable dilithium compound. Trapping of this intermediate with several electrophiles (alkyl halides, carbonyl derivatives, CO2) was successful. The extension of this procedure to several substituted phthalans (1b-i) was investigated, and the regiochemistry as well as the synthetic usefulness of these reactions are discussed.
Synthesis of α-Hydroxy Ketones by Direct, Low-Temperature, in Situ Nucleophilic Acylation of Aldehydes and Ketones by Acyllithium Reagents
Seyferth, Dietmar,Weinstein, Robert M.,Hui, Richard C.,Wang, Wei-Liang,Archer, Colin M.
, p. 5620 - 5629 (2007/10/02)
The reaction of n-, sec-, and tert-butyllithium with CO at atmospheric pressure at -110 and -135 deg C in the appropriate solvent system in the presence of ketones and aldehydes generates the acyllithium, RC(O)Li, which reacts with the carbonyl compound to give the α-hydroxy ketone, generally in good yield.Reactions with aldehydes are limited in scope, working well with the t-BuLi-derived acyllithium reagents, but not with n-BuC(O)Li.
