Nucleophilic borylation of aldehydes and conjugated carbonyls: Applications to homologation and carbosilylation reactions

醛和共轭羰基的亲核硼化：在同系化和碳硅烷化反应中的应用

• 批准号: 9231765
• 负责人: Timothy B Clark
• 金额: $ 38.03万
• 依托单位: UNIVERSITY OF SAN DIEGO
• 依托单位国家: 美国
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-09-16 至 2020-08-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/9231765
• 关键词: Alcohols; Aldehydes; Area; Attention; Biological; Boron; Carbon; Complex; Copper; Development; Esters; Ethers; Goals; Investigation; Ketones; Lead; Methodology; Methods; Outcome; Pharmaceutical Preparations; Pharmacologic Substance; Process; Protocols documentation; Reaction; Research; Scheme; Silanes; Silicon; Source; Structure; Testing; Universities; Washington; Work; abstracting; base; enol; functional group; novel strategies; nucleophilic addition; oxidation; pi bond; small molecule; stereochemistry; success

Project Summary/Abstract Lead-PI: Timothy Clark University of San Diego Sub-PI: Gregory O'Neil Western Washington University Title: Nucleophilic borylation of aldehydes and conjugated carbonyls: Applications to homologation and carbosilylation reactions Abstract: The proposed research involves the development of synthetic methods that utilize the copper- catalyzed nucleophilic borylation of aldehydes and ,-unsaturated carbonyls. The resulting organoboronate esters will be used as intermediates in two types of synthetic reactions: (1) homologation of the carbon–boron bond with complex homologating agents; (2) oxidation to set up intramolecular carbosilylations to form tertiary alcohols stereoselectively. These two approaches to preparing synthetically useful and highly-substituted organic intermediates will simplify access to a number of biologically relevant targets. The versatility and selectivities afforded by these new methods will prove superior for a number of synthetic applications. The two major aims of this project are: 1. Utilize aldehyde borylation/homologations to construct highly-substituted organoboronate esters with contiguous stereocenters. 2. Develop intramolecular carbosilylations of -hydroxyketones using tethered silanes.

项目概要/摘要 首席 PI：Timothy Clark 圣地亚哥大学 副 PI：Gregory O'Neil 西华盛顿大学 标题：醛和共轭羰基的亲核硼化：在同系化和共轭化中的应用 羧化反应 摘要：所提出的研究涉及利用铜的合成方法的开发 催化醛和α,β-不饱和羰基的亲核硼化反应生成有机硼酸酯。 酯将用作两类合成反应的中间体：（1）碳-硼的同系化 与复杂的同系剂结合；（2）氧化形成分子内碳甲硅烷基化形成三级结构 这两种方法可以立体选择性地制备合成有用的和高度取代的醇。 有机中间体将简化获得许多生物学相关目标的多功能性和。 这些新方法所提供的选择性对于许多合成应用来说都具有优越性。 该项目的两个主要目标是： 1. 利用醛硼化/同系化构建高度取代的有机硼酸酯 连续的立体中心。 2. 使用束缚硅烷开发 -羟基酮的分子内碳甲硅烷基化。

项目成果

Chemoselective Carbonyl Allylations with Alkoxyallylsiletanes.

烷氧基烯丙基硅烷的化学选择性羰基烯丙基化。

• DOI: 10.1021/acs.joc.8b03028
• 发表时间: 2019
• 期刊: The Journal of organic chemistry
• 作者: Spaltenstein,Paul;Cummins,ElizabethJ;Yokuda,Kelly-Marie;Kowalczyk,Tim;Clark,TimothyB;O'Neil,GregoryW
• 通讯作者: O'Neil,GregoryW

Catalytic and regulatory effects of light intensity on chloroplast ATP synthase.

光强度对叶绿体 ATP 合酶的催化和调节作用。

• DOI: 10.1021/bi00379a040
• 发表时间: 1987
• 期刊: Biochemistry
• 影响因子: 2.9
• 作者: Stroop,SD;Boyer,PD
• 通讯作者: Boyer,PD

β-Silyloxy Allylboronate Esters through an Aldehyde Borylation/Homologation Sequence.

通过醛硼化/同系化序列生成β-甲硅烷氧基烯丙基硼酸酯。

• DOI: 10.1016/j.tetlet.2020.152082
• 发表时间: 2020
• 期刊: Tetrahedron letters
• 影响因子: 1.8
• 作者: Meyer,GillianF;Nistler,MaggieA;Samoshin,AndreyV;McManus,BrennanD;Thane,TaylorA;Ferber,CarlJ;O'Neil,GregoryW;Clark,TimothyB
• 通讯作者: Clark,TimothyB

Iodine-mediated rearrangements of diallylsilanes.

碘介导的二烯丙基硅烷重排。

• DOI: 10.1016/j.tetlet.2017.07.045
• 发表时间: 2017
• 期刊: Tetrahedron letters
• 影响因子: 1.8
• 作者: O'Neil,GregoryW;Cummins,ElizabethJ
• 通讯作者: Cummins,ElizabethJ

Sequential iodine-mediated diallylsilane rearrangement/asymmetric dihydroxylation: Synthesis and reactions of enantioenriched oxasilacycles.

连续碘介导的二烯丙基硅烷重排/不对称二羟基化：对映​​体富集的草硅环的合成和反应。

• DOI: 10.1016/j.tetlet.2021.153392
• 发表时间: 2021
• 期刊: Tetrahedron letters
• 影响因子: 1.8
• 作者: Myers,ChristopherR;Spaltenstein,Paul;Baker,LaurenK;Schwans,CodyL;Clark,TimothyB;O'Neil,GregoryW
• 通讯作者: O'Neil,GregoryW