62839-71-8Relevant academic research and scientific papers
Pd-catalyzed oxidative Heck-type arylation of vinyl ketones, alkenes, and acrylates with Sb-aryl-tetrahydrodibenz[c,f][1,5]azastibocines
Murata, Yuki,Kakusawa, Naoki,Arakawa, Yukako,Hayashi, Yukako,Morinaga, Shun,Ueda, Masaaki,Hyodo, Tadashi,Matsumura, Mio,Yamaguchi, Kentaro,Kurita, Jyoji,Yasuike, Shuji
, (2020/10/18)
The Pd-catalyzed cross-coupling reactions of Sb-aryl-1,5-azastibocines with alkenes are described. The reactions of azastibocines with alkenes such as vinyl ketones, alkenes, and acrylates in the presence of 10 mol% PdCl2 at 80 °C in DMA under aerobic conditions produced Heck adducts in moderate-to-excellent yields. Single-crystal X-ray and NMR analysis revealed that the aryl donors in this reaction, the Sb-aryl-1,5-azastibocines, are hypervalent compounds that display N–Sb intramolecular non-bonding interaction. These are the first examples of Pd-catalyzed Heck-type arylations using heterocyclic hypervalent organoantimony compounds. Although the reactions proceeded efficiently with the azastibocines, they hardly progressed with trivalent and pentavalent triarylantimony reagents.
Iterative synthesis of alkenes by insertion of lithiated epoxides into boronic esters
Bojaryn, Kevin,Fritsch, Stefan,Hirschhaüser, Christoph
supporting information, p. 2218 - 2222 (2019/04/10)
The insertion of lithiated epoxides into boronic esters followed by thermal syn-elimination provides a stereospecific entry to alkenes. This process avoids transition metals and is amenable to iteration to provide higher substitution patterns.
Metal-Catalyzed Remote Functionalization of ω-Ene Unsaturated Ethers: Towards Functionalized Vinyl Species
Ho, Guo-Ming,Judkele, Lina,Bruffaerts, Jeffrey,Marek, Ilan
, p. 8012 - 8016 (2018/06/29)
The combined ruthenium-catalyzed chain walking with the nickel-catalyzed cross-coupling reaction of ω-alkenyl ethers provide a unique entry to functionalized vinyl species. This transformation illustrates the power and flexibility of remote functionalization by demonstrating the compatibility of two independent reactions involving unrelated sites.
Palladium/Light induced radical alkenylation and allylation of alkyl iodides using alkenyl and allylic sulfones
Sumino, Shuhei,Uno, Misae,Huang, Hsin-Ju,Wu, Yen-Ku,Ryu, Ilhyong
supporting information, p. 1078 - 1081 (2018/02/23)
Alkenylation and allylation of alkyl iodides with alkenyl and allyl sulfones, respectively, took place under Pd/photoirradiation system. The initial alkyl radical, derived from a single electron transfer between Pd(0) and RI, underwent the title transformations. Pd(0) was regenerated through a reductive elimination of PhSO2PdI, which is formed by the combination of the sulfonyl radical and the palladium radical. The addition of water was effective, presumably by pushing the equilibrium through hydrolysis of PhSO2I.
N-Acylsaccharins as Amide-Based Arylating Reagents via Chemoselective N-C Cleavage: Pd-Catalyzed Decarbonylative Heck Reaction
Liu, Chengwei,Meng, Guangrong,Szostak, Michal
, p. 12023 - 12030 (2016/12/09)
Palladium-catalyzed decarbonylative Heck reaction of amides by chemoselective N-C activation using N-acylsaccharins as coupling partners has been accomplished. These studies represent only the second example of amide-Heck reactions reported to date. A broad range of electronically diverse amide and olefin coupling partners is amenable to this transformation. Orthogonal site-selective Heck cross-couplings by C-Br/N-C cleavage and mechanistic studies are reported. This report introduces readily available, bench-stable, cheap, and benign N-acylsaccharins as aryl transfer reagents to access versatile aryl-metal intermediates.
Z -selective olefin synthesis via iron-catalyzed reductive coupling of alkyl halides with terminal arylalkynes
Cheung, Chi Wai,Zhurkin, Fedor E.,Hu, Xile
supporting information, p. 4932 - 4935 (2015/05/05)
Selective catalytic synthesis of Z-olefins has been challenging. Here we describe a method to produce 1,2-disubstituted olefins in high Z selectivity via reductive cross-coupling of alkyl halides with terminal arylalkynes. The method employs inexpensive and nontoxic catalyst (iron(II) bromide) and reductant (zinc). The substrate scope encompasses primary, secondary, and tertiary alkyl halides, and the reaction tolerates a large number of functional groups. The utility of the method is demonstrated in the synthesis of several pharmaceutically relevant molecules. Mechanistic study suggests that the reaction proceeds through an iron-catalyzed anti-selective carbozincation pathway.
Palladium-catalyzed heck-type cross-couplings of unactivated alkyl iodides
McMahon, Caitlin M.,Alexanian, Erik J.
supporting information, p. 5974 - 5977 (2014/06/10)
A palladium-catalyzed, intermolecular Heck-type coupling of alkyl iodides and alkenes is described. This process is successful with a variety of primary and secondary unactivated alkyl iodides as reaction partners, including those with hydrogen atoms in t
Synthesis and structure of cobalt(II) iodide bearing a bulky N-heterocyclic carbene ligand, and catalytic activation of bromoalkanes
Matsubara, Kouki,Kumamoto, Aya,Yamamoto, Hitomi,Koga, Yuji,Kawata, Satoshi
, p. 44 - 49 (2013/03/28)
A divalent cobalt iodine complex bearing 1,3-bis(mesityl)imidazol-2-ylidene and pyridine ligands was synthesized and its structure was determined. The cobalt center has a typical d7-tetrahedral geometry, as expected. Catalytic application of this cobalt complex with bromoalkanes and Grignard reagents demonstrated high-yield formation of alkenes as a result of β-hydrogen elimination; in sharp contrast, the activation of alkyl halides was not successful using the larger N-heterocyclic carbene ligand, 1,3-bis(2,6-diisopropyl-phenyl)imidazol-2-ylidene. In the presence of styrene, Heck reaction proceeded with trans selectivity. The reaction of a substrate containing a bromobenzyl moiety yielded a homocoupling product.
Pd-catalyzed cross-coupling reactions exhibiting catalyst turnover numbers (TONs) exceeding one million
Xu, Shiqing,Truex, Nicholas L.,Mohan, Swathi,Negishi, Ei-Ichi
, p. 242 - 252 (2013/01/16)
Pd-catalyzed cross-coupling giving aryl-aryl, alkenyl-aryl, aryl-alkenyl, alkynyl-aryl, and alkynyl-alkenyl products exhibited ultra-high turnover numbers (TONs) of 0.7×107～0.69×109 by using organozincs generated in situ by treatment of the corresponding organolithiums with dry ZnBr2. Additionally, the hydrozirconation.Pd-catalyzed cross-coupling tandem processes via treatment of 1-alkynes with iBu2AlH-ZrCp2Cl2 followed by selective (≥98%) alkenyl.alkenyl coupling with either (E)- or (Z)-ethyl 3-bromoacrylate exhibited high TONs of 0.9×105～0. 81×107. Furthermore, Pd-catalyzed cross-coupling of 2-thienylzinc bromide and 1-iodo-4-nitrobenzene also showed a high TON of 0.87×105. ARKAT-USA, Inc.
Preparation of alkylmagnesium reagents from alkenes through hydroboration and boron-magnesium exchange
Reichle, Markus A.,Breit, Bernhard
supporting information; experimental part, p. 5730 - 5734 (2012/08/14)
Tolerant: Alkylmagnesium reagents can be synthesized from alkenes through a sequence of hydroboration and subsequent boron-magnesium exchange using a method that tolerates different functional groups (see scheme). The resulting alkylmagnesium reagents can be used in carbon-carbon bond forming reactions, such as alkylation reactions or transition-metal-catalyzed cross-coupling reactions. Copyright
