A concise synthesis of carpanone using solid-supported reagents and scavengers
作者:Ian R. Baxendale、Ai-Lan Lee、Steven V. Ley
DOI:10.1039/b203388g
日期:2002.8.8
Polymer-supported reagents have been applied to the synthesis of the natural product carpanone resulting in a clean and efficient synthesis without the requirement for conventional purification techniques. A new polymer-supported transition metal isomerisation catalyst is also reported.
3-Carbonylamino-8-aminoisoquinoline compounds of formula (I):
variations thereof, and their use as inhibitors of HPK1 (hematopoietic kinase 1) are described. The compounds are useful in treating HPK1-dependent disorders and enhancing an immune response. Also described are methods of inhibiting HPK1, methods of treating HPK1-dependent disorders, methods for enhancing an immune response, and methods for preparing the 3-carbonylamino-8-aminoisoquinoline compounds.
Vinylethers can be protonated to generate oxocarbenium ions that react with Me3SiCN to form cyanohydrin alkylethers. Reactions that form racemic products proceed efficiently upon conversion of the vinylether to an α-chloro ether prior to cyanide addition in a pathway that proceeds through Brønsted acid-mediated chloride ionization. Enantiomerically enriched products can be accessed by directly protonating
乙烯基醚可以质子化以生成氧代碳正离子,该离子与 Me 3 SiCN反应形成氰醇烷基醚。在通过布朗斯台德酸介导的氯离子电离进行的途径中,在加入氰化物之前将乙烯基醚转化为 α-氯醚后,形成外消旋产物的反应有效进行。可以通过用手性布朗斯台德酸直接质子化乙烯基醚以形成手性离子对来获得对映体富集的产品。Me 3 SiCN 作为亲核试剂,PhOH 在不对称双分子亲核加成到氧碳鎓离子的罕见例子中作为化学计量质子源。计算研究为催化剂和氧代碳正离子之间的相互作用提供了模型。
(NHC)NiH-Catalyzed Regiodivergent Cross-Hydroalkenylation of Vinyl Ethers with α-Olefins: Syntheses of 1,2- and 1,3-Disubstituted Allyl Ethers
作者:Weihao Chen、Yang Li、Yang Chen、Chun-Yu Ho
DOI:10.1002/anie.201712693
日期:2018.3.1
(i.e., 1 as acceptor and 2 as donor) was controlled mostly by electronic effects through the catalyst–substrate interaction. Sterically bulkier alkenes (2) were used as preferred donors compared to smaller alkenes. This electronic effect also served as a basis for the first tail‐to‐head cross‐hydroalkenylations of 1 with either a vinyl silane or boronic ester.
乙烯基醚(1)与α-烯烃(2)的交叉氢化烯基化首先通过一组[NHC-Ni(烯丙基)] BAr F(NHC = N-杂环卡宾)催化剂实现。通过使用不同尺寸的NHC,可以高度选择性地获得1,2-和1,3-二取代的烯丙基醚。相比之下,化学选择性(即1为受体,2为施主)主要受催化剂与底物相互作用的电子效应控制。与较小的烯烃相比,在立体上较大的烯烃(2)被用作优选的给体。这种电子效应也作为第一尾-头横hydroalkenylations的基础1 与乙烯基硅烷或硼酸酯。
Encapsulated molecular catalysts in polysiloxane gels: ruthenium cluster-catalyzed isomerization of alkenes
gels are prepared by treatment of polymethylhydrosiloxane with diols in the presence of (mu(3),eta(2),eta(3),eta(5)-acenaphthylene)Ru(3)(CO)(7), and act as reusable catalysts in the isomerization of alkenes without leakage of the catalyst species.