63553-63-9Relevant academic research and scientific papers
Kinetic Resolution of α-Silyl-Substituted Allylboronate Esters via Chemo- and Stereoselective Allylboration of Aldehydes
Park, Jinyoung,Jung, Yongsuk,Kim, Jeongho,Lee, Eunsung,Lee, Sarah Yunmi,Cho, Seung Hwan
supporting information, p. 2371 - 2376 (2020/12/01)
We describe the kinetic resolution of α-silyl-substituted allylboronate esters via chiral phosphoric acid-catalyzed chemo-, diastereo- and enantioselective allylboration of aldehydes. This process provides two synthetically versatile enantioenriched compo
Catalytic Allylation of Aldehydes Using Unactivated Alkenes
Tanabe, Shun,Mitsunuma, Harunobu,Kanai, Motomu
supporting information, p. 12374 - 12381 (2020/07/14)
Simple feedstock organic molecules, especially alkenes, are attractive starting materials in organic synthesis because of their wide availability. Direct utilization of such bulk, inert organic molecules for practical and selective chemical reactions, however, remains limited. Herein, we developed a ternary hybrid catalyst system comprising a photoredox catalyst, a hydrogen-atom-transfer catalyst, and a chromium complex catalyst, enabling catalytic allylation of aldehydes with simple alkenes, including feedstock lower alkenes. The reaction proceeded under visible-light irradiation at room temperature and with high functional group tolerance. The reaction was extended to an asymmetric variant by employing a chiral chromium complex catalyst.
Photoredox Ni-Catalyzed Branch-Selective Reductive Coupling of Aldehydes with 1,3-Dienes
Chen, Jie,Gu, Zheng-Yang,Li, Wen-Duo,Li, Yan-Lin,Xia, Ji-Bao
, p. 1528 - 1534 (2020/02/04)
We report here a Ni-catalyzed reductive coupling of aldehydes with widely available 1,3-dienes under visible-light photoredox dual catalysis. The homoallyic alcohols are obtained in broad scope with complete branched regioselectivity. Hantzsch ester is used as the hydrogen radical source to oxidize low-valent nickel salt affording Ni-H species. Preliminary mechanistic studies indicate a successive single-electron transfer (SET) pathway and the generation of a key π-allylnickel intermediate via Ni-H insertion of 1,3-diene in this synergistic catalytic process.
Bi(cyclopentyl)diol-Derived Boronates in Highly Enantioselective Chiral Phosphoric Acid-Catalyzed Allylation, Propargylation, and Crotylation of Aldehydes
Yuan, Jinping,Jain, Pankaj,Antilla, Jon C.
, p. 12988 - 13003 (2020/11/23)
In this study, we disclose the catalytic addition of bi(cyclopentyl)diol-derived boronates to aldehydes promoted by chiral phosphoric acids, allowing for the formation of enantioenriched homoallylic, propargylic, and crotylic alcohols (up to >99% enantiom
Active bismuth mediated allylation of carbonyls/N-tosyl aldimines and propargylation of aldehydes in water
Sawkmie, Micky Lanster,Paul, Dipankar,Khatua, Snehadrinarayan,Chatterjee, Paresh Nath
, (2019/06/08)
Abstract: Active bismuth is synthesized by the chemical reduction of bismuth trichloride using freshly prepared sodium stannite solution as the reducing agent at room temperature. The as-synthesized active bismuth is applied as a reagent for the synthesis of homoallyl alcohol/homopropargyl alcohol from allyl bromide/propargyl bromide and carbonyl compounds in water at 50°C. The homoallyl amines are also synthesized from N-tosyl aldimines and allyl bromide using active bismuth reagent in good yields. No assistance of organic co-solvent, co-reagent, phase transfer catalyst or inert atmosphere is required for this reaction. The waste bismuth material obtained after the completion of the organic reaction can be reduced to active bismuth by sodium stannite solution and successfully reused for mediating the allylation of aldehydes. Graphical Abstract:: Synopsis Active bismuth mediated allylation/crotylation of aldehydes is developed in water to get homoallyl alcohols. The method is also applied for the allylation of N-tosyl aldimines and propargylation of aldehydes in water to achieve the homoallyl amines and homopropargyl alcohols, respectively. The reactions do not require the assistance of organic co-solvent, co-reagent, phase transfer catalyst or inert atmosphere.[Figure not available: see fulltext.].
Stereodivergent total synthesis of Br-nannocystins underpinning the polyketide (10R,11S) configuration as a key determinant of potency
Tian, Yunfeng,Wang, Jiyan,Liu, Wenjie,Yuan, Xiaoya,Tang, Yang,Li, Jing,Chen, Yue,Zhang, Weicheng
, p. 568 - 578 (2019/01/21)
Continuing our investigation into the structure-activity relationship of antiproliferative macrocyclic nannocystins, we describe herein total synthesis of all four stereoisomers of Br-nannocystins as well as a simplified analogue varying at the polyketide C10 and C11 positions. Biological evaluation of these compounds against PANC1 cancer cell lines showed that both the (10R,11S) configuration and its associated two substituents are crucial for high potency.
Novel nannocystin A analogues as anticancer therapeutics: Synthesis, biological evaluations and structure–activity relationship studies
Liu, Qiang,Yang, Xiaohong,Ji, Jie,Zhang, Shao-Lin,He, Yun
, p. 99 - 111 (2019/03/17)
Nannocystin A is a novel 21-membered macrocyclic lactam that targets eukaryotic translation elongation factor 1α (eEF1A) and displays potent antiproliferative activities. Herein, a series of nannocystin A analogues were synthesized and their structure–activity relationship (SAR) were established based on the MTT assay and western blotting analysis. The SAR enabled us to identify a structurally simplified nannocystin A analogue LQ18, which exhibited potent antiproliferative activities with IC50 values ranging from 4.3 to 48 nM against the tested cell lines, and inhibited eEF1A1 expression in A549 cell line. LQ18 arrested cell cycle at G2 phase and induced A549 cell apoptosis via up-regulation of caspase-3, caspase-9 and bax protein expressions in a dose-dependent manner, while it significantly decreased the bcl-2 expression. Collectively, these data demonstrated that LQ18 could be a promising lead for the development of structurally novel eEF1A1 inhibitor for cancer treatment.
Indium-mediated allylation of carbonyl compounds in ionic liquids: Effect of salts in ionic liquids
Hirashita, Tsunehisa,Takahashi, Fusako,Noda, Takayuki,Takagi, Yuji,Araki, Shuki
, p. 1 - 9 (2018/07/31)
The In-mediated allylation of carbonyl compounds can be performed in various types of solvents including ionic liquids. However, we have found that in [bmim][BF4] (where bmim = 1-butyl-3-methylimidazolium), the In-mediated coupling of crotyl bromide with benzaldehyde gives a complex mixture, and some additives, such as halides and amines, are crucial for the successful conversion to the corresponding γ-adduct. Instead, the addition of alcohols or water promotes the formation of the α-adduct. An asymmetric induction with up to 62% enantiomeric excess (ee) was observed employing cinchonidine as an additive in a binary solvent consisting of an ionic liquid and dichloromethane.
Catalytic Nucleophilic Allylation Driven by the Water-Gas Shift Reaction
Denmark, Scott E.,Matesich, Zachery D.,Nguyen, Son T.,Milicevic Sephton, Selena
supporting information, p. 23 - 48 (2018/02/19)
The ruthenium-catalyzed allylation of aldehydes with allylic pro-nucleophiles has been demonstrated to be an efficient means to form carbon-carbon bonds under mild conditions. The evolution of this reaction from the initial serendipitous discovery to its general synthetic scope is detailed, highlighting the roles of water, CO, and amine in the generation of a more complete catalytic cycle. The use of unsymmetrical allylic pro-nucleophiles was shown to give preferential product formation through the modulation of reaction conditions. Both (E)-cinnamyl acetate and vinyl oxirane were efficiently used to form the anti-branched products (up to >20:1 anti/syn) and E-linear products (up to >20:1 E/Z) in high selectivity with aromatic, α,β-unsaturated, and aliphatic aldehydes, respectively. Attempts to render the reaction enantioselective are highlighted and include enantioenrichment of up to 75:25 for benzaldehyde.
