Reductive Coupling between C–N and C–O Electrophiles
作者:Rong-De He、Chun-Ling Li、Qiu-Quan Pan、Peng Guo、Xue-Yuan Liu、Xing-Zhong Shu
DOI:10.1021/jacs.9b05224
日期:2019.8.14
The cross-electrophile reaction is a promising strategy for C-C bond formation. Recent studies have focused mainly on reactions with organic halides. Here we report a coupling reaction between C-N and C-O electrophiles that demonstrates the possibility of constructing a C-C bond via C-N and C-O cleavage. Several reactions between benzyl/aryl ammonium salts and vinyl/aryl C-O electrophiles have been
交叉亲电反应是 CC 键形成的一个有前景的策略。最近的研究主要集中在与有机卤化物的反应上。在这里,我们报告了 CN 和 CO 亲电试剂之间的偶联反应,证明了通过 CN 和 CO 裂解构建 CC 键的可能性。已经研究了苄基/芳基铵盐和乙烯基/芳基 CO 亲电试剂之间的几种反应。初步机理研究表明,苄基铵是通过自由基机制活化的。
Nitro <i>seco</i> Analogues of the Duocarmycins Containing Sulfonate Leaving Groups as Hypoxia-Activated Prodrugs for Cancer Therapy
作者:Ralph J. Stevenson、William A. Denny、Moana Tercel、Frederik B. Pruijn、Amir Ashoorzadeh
DOI:10.1021/jm201717y
日期:2012.3.22
of 19 (5-nitro-2,3-dihydro-1H-benzo[e]indol-1-yl)methyl sulfonate prodrugs containing sulfonateleavinggroups and 7-substituted electron-withdrawing groups is reported. These were designed to undergo hypoxia-selective metabolism to form potent DNA minor groove-alkylating agents. Analogues 17 and 24, containing the benzyl sulfonateleavinggroup and a neutral DNA minor groove-binding side chain, displayed
报道了19(5-硝基-2,3-二氢-1 H-苯并[ e ]吲哚-1-基)甲基磺酸盐前药的合成,该药物含有磺酸盐离去基团和7-取代的吸电子基团。这些被设计用于进行缺氧选择性代谢,以形成有效的DNA小沟烷基化剂。类似物17和24,包含磺酸苄酯离去基团和中性DNA小沟结合侧链,在体外抗增殖试验中显示HT29人癌细胞的缺氧细胞毒性比(HCR)> 1000。四个类似物在一组八种人类癌细胞系中维持较大的HCR。在克隆形成分析中,19HT29细胞的HCR显示为4090。还制备了十种可溶性磷酸盐前药,并以无毒剂量在体内,单独或与放射联合在SiHa人肿瘤异种移植物中进行了评估。化合物34和39的缺氧log 10细胞杀伤(LCK)分别为1.78和2.71,与先前报道的氯化物或溴化物类似物具有同等或更高的活性,因此显示出作为缺氧激活的前药的杰出前景。
Stabilized and Destabilized Carbocations in the 1,6-Methano[10]annulene Series
作者:Xavier Creary、Kevin Miller
DOI:10.1021/jo035006w
日期:2003.10.1
2-Chloromethyl and 3-chloromethyl-1,6-methano[10]annulenesystems solvolyze in methanol to give simple substitution products. Solvent effect studies and the special salt effect support the involvement of cationic intermediates stabilized by the 1,6-methano[10]annulene group. Rate data indicate that the degree of cation stabilization greatly exceeds that of naphthyl groups. B3LYP/6-31G computational
Directing Selectivity to Aldehydes, Alcohols, or Esters with Diphobane Ligands in Pd-Catalyzed Alkene Carbonylations
作者:Dillon W. P. Tay、James D. Nobbs、Srinivasulu Aitipamula、George J. P. Britovsek、Martin van Meurs
DOI:10.1021/acs.organomet.1c00228
日期:2021.6.28
trifluoromethylphenylene-bridged diphobane L1 with an electron-withdrawing substituent, lead to ester products via alkoxycarbonylation, whereas BCOPE gives predominantly alcohol products (n-nonanol and isomers) via reductive hydroformylation. The preference of BCOPE for reductive hydroformylation is also seen in the hydroformylation of 1-hexene in diglyme as the solvent, producing heptanol as the major product, whereas
Process for halomethyl ethers of hydroxyiminomethyl quaternary pyridinium salts
申请人:Huang Der-Shing
公开号:US20060183777A1
公开(公告)日:2006-08-17
A halide salt of a 1-(hydroxyiminomethyl-1-pyridino)-3-(halomethyl)-2-oxapropane is prepared by adding a pyridinealdoxime to a bis-halomethylether in such a manner that the bis-halomethylether is maintained in excess throughout the addition. This procedure produces the halide salt of a 1-(hydroxyiminomethyl-1-pyridino)-3-(halomethyl)-2-oxapropane in high yield and purity, which facilitates its use as an intermediate in the manufacture of an asymmetrically substituted 1,3-di (1-pyridino)-2-oxapropane, a class of compounds that are generally useful antidotes to various toxic agents. A prominent member of the class is the dimethylsulfonate salt of 1-(2-hydroxyiminomethyl-1-pyridino)-3-(4-carbamoyl-1-pyridino)-2-oxapropane. The use of mercaptoalkyl-functionalized polymers is disclosed as a preferred metal ion scavenger for a final purification step in the manufacture of these compounds.