59137-50-7Relevant academic research and scientific papers
Contra-thermodynamic Olefin Isomerization by Chain-Walking Hydroboration and Dehydroboration
Bloomer, Brandon,Butcher, Trevor W.,Ciccia, Nicodemo R.,Conk, Richard J.,Hanna, Steven,Hartwig, John F.
, p. 1005 - 1010 (2022/02/10)
We report a dehydroboration process that can be coupled with chain-walking hydroboration to create a one-pot, contra-thermodynamic, short-or long-range isomerization of internal olefins to terminal olefins. This dehydroboration occurs by a sequence comprising activation with a nucleophile, iodination, and base-promoted elimination. The isomerization proceeds at room temperature without the need for a fluoride base, and the substrate scope of this isomerization is expanded over those of previous isomerizations we have reported with silanes.
Synthesis and evaluation of novel, selective, functionalized γ-butyrolactones as sigma-2 ligands
Blass, Benjamin E.,Blattner, Kevin M.,Canney, Daniel J.,Gao, Rong,Gordon, John C.,Pippin, Douglas A.
, p. 337 - 349 (2022/01/19)
The sigma-2 (σ2) receptor was discovered nearly 40 years ago and was recently identified as the Transmembrane Protein 97 (TMEM97, also known as MAC30 (Meningioma-associated protein)). Aberrant σ2 activity has been linked to diseases
Diethylzinc-Mediated Radical 1,2-Addition of Alkenes and Alkynes
Li, Xin,He, Songtao,Song, Qiuling
supporting information, p. 2994 - 2999 (2021/05/04)
A novel diethylzinc-mediated radical 1,2-addition of perfluoroalkyl iodides to unactivated alkenes and alkynes is presented, which demonstrates a novel way to generate an ethyl difluoroacetate radical. This method is highly efficient and gives full conversions of the substrates, high yields of the products, and negligible byproducts and requires no column chromatography purifications. The mild conditions enable this protocol to exhibit excellent functional group compatibility.
Complex Polyheterocycles and the Stereochemical Reassignment of Pileamartine A via Aza-Heck Triggered Aryl C-H Functionalization Cascades
Bower, John F.,Caiger, Lewis,García-Cárceles, Javier,Hazelden, Ian R.,Jones, Benjamin T.,Langer, Thomas,Lewis, Richard J.
supporting information, p. 15593 - 15598 (2021/10/12)
Structurally complex benzo- and spiro-fused N-polyheterocycles can be accessed via intramolecular Pd(0)-catalyzed alkene 1,2-aminoarylation reactions. The method uses N-(pentafluorobenzoyloxy)carbamates as the initiating motif, and this allows aza-Heck-type alkene amino-palladation in advance of C-H palladation of the aromatic component. The chemistry is showcased in the first total synthesis of the complex alkaloid (+)-pileamartine A, which has resulted in the reassignment of its absolute stereochemistry.
Zirconium-catalysed direct substitution of alcohols: enhancing the selectivity by kinetic analysis
Camaj, David,Carlsson, Robin,Dalla-Santa, Oscar,Lill, Malin,Lundberg, Helena,Margarita, Cristiana,Ramstr?m, Anja,Tu?on, Hernando,Villo, Piret
, p. 7420 - 7430 (2021/11/23)
Kinetic analysis was used as a tool for rational optimization of a catalytic, direct substitution of alcohols to enable the selective formation of unsymmetrical ethers, thioethers, and Friedel-Crafts alkylation products using a moisture-tolerant and commercially available zirconium complex (2 to 8 mol%). Operating in air and in the absence of dehydration techniques, the protocol furnished a variety of products in high yields, including glycosylated alcohols and sterically hindered ethers. In addition, the kinetic studies provided mechanistic insight into the network of parallel transformations that take place in the reaction, and helped to elucidate the nature of the operating catalyst.
First Stereoselective Total Synthesis of Modiolin
Rao, G. Padma,Mohan, B. Sathish,Siddaiah
, p. 2028 - 2031 (2021/01/13)
Abstract: The first stereoselective total synthesis of the linear pentaketide Modiolin has been performed via Jacobsen’ hydrolytic kinetic resolution and 2C-Wittig homologation as key steps.
Metal-Catalyzed Remote Functionalization of ω-Ene Unsaturated Ethers: Towards Functionalized Vinyl Species
Ho, Guo-Ming,Judkele, Lina,Bruffaerts, Jeffrey,Marek, Ilan
supporting information, 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.
Total Synthesis and Cytotoxic Activity of 5′-Hydroxyzearalenone and 5′β-Hydroxyzearalenone
Thiraporn, Aticha,Rukachaisirikul, Vatcharin,Iawsipo, Panata,Somwang, Tatiyar,Tadpetch, Kwanruthai
supporting information, p. 7133 - 7147 (2017/12/28)
An efficient and convergent synthesis of 5′-hydroxyzearalenone and 5′β-hydroxyzearalenone, 14-membered β-resorcylic acid lactone (RAL) natural products, has been achieved in a longest linear sequence of 19 steps, and a total of 29 steps, starting from commercially available 5-hexen-1-ol and methyl 2-(3,5-dimethoxyphenyl)acetate. The key features of our synthesis include a Jacobsen hydrolytic kinetic resolution, a Mitsunobu esterification and (an E)-selective ring-closing metathesis (RCM). Our synthesis also highlights the utility of the acetal protecting group for the resorcylate moiety, and its compatibility with RCM reactions for the synthesis of 14-membered RALs. The cytotoxic activity of both synthetic compounds was evaluated against seven human cancer cell lines. 5′-Hydroxyzearalenone shows more potent cytotoxic activity against most of the cancer cell lines tested than its epimer, 5′β-hydroxyzearalenone. Both compounds show significant cytotoxic activity against the C33A cervical cancer cell line, with IC50 values of 21.33 ± 6.43 μm and 16.00 ± 12.17 μm, respectively.
Stereoselective synthesis of dendrodolide-L
Bujaranipalli, Sheshurao,Das, Saibal
, p. 254 - 260 (2017/03/01)
An efficient stereoselective total synthesis of 12-membered macrolide dendrodolide L has been achieved. The key reactions involved are Keck asymmetric allylation, Jacobsen's hydrolytic kinetic resolution, Sharpless asymmetric epoxidation, Mitsunobu reaction and ring-closing metathesis reaction.
Copper-Catalyzed Oxyboration of Unactivated Alkenes
Itoh, Taisuke,Matsueda, Takumi,Shimizu, Yohei,Kanai, Motomu
supporting information, p. 15955 - 15959 (2015/11/03)
The first regiodivergent oxyboration of unactivated terminal alkenes is reported, using copper alkoxide as a catalyst, bis(pinacolato)diboron [(Bpin)2] as a boron source, and (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) as an oxygen source. The reaction is compatible with various functional groups. Two regioisomers are selectively produced by selecting the appropriate ligands on copper. The products may be used as a linchpin precursor for various other functionalizations, and net processes such as carbooxygenation, aminooxygenation, and dioxygenation of alkenes can be achieved after C-B bond transformations. Mechanistic studies indicate that the reaction involves the following steps: 1)Transmetalation between CuOtBu and (Bpin)2 to generate a borylcopper species; 2)regiodivergent borylcupration of alkenes; 3) oxidation of the thus-generated C-Cu bond to give an alkyl radical; 4)trapping of the resulting alkyl radical by TEMPO.
