钌催化异戊二烯与杂芳族仲醇的氢羟烷基化反应：推定金属环中间体的分离及可逆形成
Ruthenium catalyzed hydrohydroxyalkylation of isoprene with heteroaromatic secondary alcohols: isolation and reversible formation of the putative metallacycle intermediate.
作者信息
Park Boyoung Y, Montgomery T Patrick, Garza Victoria J, Krische Michael J
机构信息
University of Texas at Austin , Department of Chemistry and Biochemistry, Austin, Texas 78712, United States.
出版信息
J Am Chem Soc. 2013 Nov 6;135(44):16320-3. doi: 10.1021/ja4087193. Epub 2013 Oct 24.
Abstract
Heteroaromatic secondary alcohols react with isoprene to form products of hydrohydroxyalkylation in the presence of ruthenium(0) catalysts generated from Ru3(CO)12 and tricyclohexylphosphine, enabling direct conversion of secondary to tertiary alcohols in the absence of premetalated reagents or stoichiometric byproducts. The putative oxaruthenacycle intermediate has been isolated and characterized, and reversible metallacycle formation has been demonstrated.
摘要
在由Ru₃(CO)₁₂和三环己基膦生成的钌(0)催化剂存在下，杂芳族仲醇与异戊二烯反应形成氢羟烷基化产物，从而在没有预金属化试剂或化学计量副产物的情况下实现仲醇直接转化为叔醇。已分离并表征了假定的氧钌环中间体，并证明了金属环的可逆形成。
相似文献
1
Ruthenium catalyzed hydrohydroxyalkylation of isoprene with heteroaromatic secondary alcohols: isolation and reversible formation of the putative metallacycle intermediate.钌催化异戊二烯与杂芳族仲醇的氢羟烷基化反应：推定金属环中间体的分离及可逆形成
J Am Chem Soc. 2013 Nov 6;135(44):16320-3. doi: 10.1021/ja4087193. Epub 2013 Oct 24.
2
Ruthenium catalyzed hydroaminoalkylation of isoprene via transfer hydrogenation: byproduct-free prenylation of hydantoins.钌催化异戊二烯通过转移氢化的氢氨基烷基化反应：海因衍生物的无副产物烯丙基化。
Chem Commun (Camb). 2013 Jul 11;49(54):6096-8. doi: 10.1039/c3cc43463j.
3
Uranium(IV) amido-borohydrides as highly active diene polymerisation catalysts.铀(IV)酰胺硼氢化物作为高活性二烯聚合催化剂。
Dalton Trans. 2013 Jul 7;42(25):9033-9. doi: 10.1039/c3dt50131k. Epub 2013 Apr 10.
4
Catalytic alkylation of methyl-N-heteroaromatics with alcohols.醇催化甲基-N-杂芳基化合物的烷基化反应。
J Am Chem Soc. 2010 Jan 27;132(3):924-5. doi: 10.1021/ja9095413.
5
Diastereo- and enantioselective ruthenium-catalyzed hydrohydroxyalkylation of 2-silyl-butadienes: carbonyl syn-crotylation from the alcohol oxidation level.立体选择性和对映选择性的钌催化 2-硅基丁二烯的氢氢加氧烷基化反应：醇氧化水平的羰基顺式烯丙基化。
J Am Chem Soc. 2011 Jul 13;133(27):10582-6. doi: 10.1021/ja2046028. Epub 2011 Jun 16.
6
Catalytic Enantioselective Conjugate Additions of (pin)B-Substituted Allylcopper Compounds Generated in situ from Butadiene or Isoprene.（pin）B 取代的烯丙基铜化合物的原位生成及其与丁二烯或异戊二烯的催化对映选择性共轭加成反应。
Angew Chem Int Ed Engl. 2016 Aug 16;55(34):9997-10002. doi: 10.1002/anie.201605001. Epub 2016 Jul 20.
7
Cationic rare-earth-metal half-sandwich complexes for the living trans-1,4-isoprene polymerization.用于活性反式-1,4-异戊二烯聚合的阳离子稀土金属半夹心配合物。
Angew Chem Int Ed Engl. 2008;47(4):775-8. doi: 10.1002/anie.200703514.
8
Regioselective ruthenium catalyzed hydrohydroxyalkylation of dienes with 3-hydroxy-2-oxindoles: prenylation, geranylation, and beyond.区域选择性钌催化二烯与 3-羟基-2-氧吲哚的氢氢羟烷基化反应：prenylation、香叶基化和 beyond。
Org Lett. 2013 Jun 21;15(12):2994-7. doi: 10.1021/ol401184k. Epub 2013 May 30.
9
Enantioselective C-H crotylation of primary alcohols via hydrohydroxyalkylation of butadiene.通过丁二烯的氢羟烷基化反应实现伯醇的对映选择性 C-H 丙烯基化。
Science. 2012 Apr 20;336(6079):324-7. doi: 10.1126/science.1219274. Epub 2012 Mar 22.
10
Ruthenium-catalysed oxidative synthesis of heterocycles from alcohols.钌催化的醇氧化合成杂环化合物。
Org Biomol Chem. 2012 Jan 14;10(2):240-3. doi: 10.1039/c1ob06516e. Epub 2011 Oct 28.
引用本文的文献
1
Ion-Pair Hydrogen Atom Transfer Catalysis Enables Cr-Catalyzed Allylation of Ketones Using Hydrocarbon Alkenes.离子对氢原子转移催化实现了铬催化的酮与烃类烯烃的烯丙基化反应。
Angew Chem Int Ed Engl. 2025 May;64(21):e202503249. doi: 10.1002/anie.202503249. Epub 2025 Mar 16.
2
Heteroaryl-Directed Iridium-Catalyzed Enantioselective C-H Alkenylations of Secondary Alcohols.杂芳基导向的铱催化仲醇对映选择性C-H烯基化反应
J Am Chem Soc. 2025 Jan 8;147(1):118-124. doi: 10.1021/jacs.4c16414. Epub 2024 Dec 23.
3
Catalytic Enantioselective C-C Coupling of Alcohols for Polyketide Total Synthesis beyond Chiral Auxiliaries and Premetalated Reagents.超越手性助剂和预金属化试剂的醇催化对映选择性碳-碳偶联用于聚酮全合成
Chem Rev. 2024 Dec 25;124(24):13715-13735. doi: 10.1021/acs.chemrev.4c00858. Epub 2024 Dec 6.
4
Leveraging the Stereochemical Complexity of Octahedral Diastereomeric-at-Metal Catalysts to Unlock Regio-, Diastereo-, and Enantioselectivity in Alcohol-Mediated C-C Couplings via Hydrogen Transfer.利用八面体金属中心非对映异构催化剂的立体化学复杂性，通过氢转移在醇介导的碳-碳偶联反应中实现区域、非对映和对映选择性。
J Am Chem Soc. 2024 Mar 27;146(12):7905-7914. doi: 10.1021/jacs.4c01857. Epub 2024 Mar 13.
5
Intermolecular Metal-Catalyzed C‒C Coupling of Unactivated Alcohols or Aldehydes for Convergent Ketone Construction beyond Premetalated Reagents.分子间金属催化未活化醇或醛的C-C偶联反应用于构建超越预金属化试剂的收敛性酮类化合物。
ACS Catal. 2023 Aug 18;13(16):10976-10987. doi: 10.1021/acscatal.3c02209. Epub 2023 Aug 4.
6
Copper-Catalyzed Asymmetric Acylboration of 1,3-Butadienylboronate with Acyl Fluorides.铜催化1,3 - 丁二烯硼酸酯与酰氟的不对称酰基硼化反应
Angew Chem Int Ed Engl. 2023 Oct 23;62(43):e202304796. doi: 10.1002/anie.202304796. Epub 2023 Sep 15.
7
Ligand Control in Co-Catalyzed Regio- and Enantioselective Hydroboration: Homoallyl Secondary Boronates via Uncommon 4,3-Hydroboration of 1,3-Dienes.共催化剂调控的区域和对映选择性氢硼化反应：通过 1,3-二烯的非常见 4,3-氢硼化反应得到偕二烯基次级硼酸盐。
J Am Chem Soc. 2023 Apr 5;145(13):7462-7481. doi: 10.1021/jacs.3c00181. Epub 2023 Mar 27.
8
Historical perspective on ruthenium-catalyzed hydrogen transfer and survey of enantioselective hydrogen auto-transfer processes for the conversion of lower alcohols to higher alcohols.钌催化氢转移的历史视角以及用于将低级醇转化为高级醇的对映选择性氢自动转移过程综述。
Chem Sci. 2022 Oct 26;13(43):12625-12633. doi: 10.1039/d2sc05621f. eCollection 2022 Nov 9.
9
Direct use of 1,3-dienes for the allylation of ketones catalytic hydroindation.直接使用1,3 - 二烯进行酮的烯丙基化反应——催化氢铟化反应。
RSC Adv. 2020 Feb 6;10(10):6030-6034. doi: 10.1039/d0ra00853b. eCollection 2020 Feb 4.
10
Borrowing Hydrogen for Organic Synthesis.用于有机合成的氢借用。
ACS Cent Sci. 2021 Apr 28;7(4):570-585. doi: 10.1021/acscentsci.1c00125. Epub 2021 Mar 25.
本文引用的文献
1
Regioselective ruthenium catalyzed hydrohydroxyalkylation of dienes with 3-hydroxy-2-oxindoles: prenylation, geranylation, and beyond.区域选择性钌催化二烯与 3-羟基-2-氧吲哚的氢氢羟烷基化反应：prenylation、香叶基化和 beyond。
Org Lett. 2013 Jun 21;15(12):2994-7. doi: 10.1021/ol401184k. Epub 2013 May 30.
2
Successive C-C coupling of dienes to vicinally dioxygenated hydrocarbons: ruthenium catalyzed [4 + 2] cycloaddition across the diol, hydroxycarbonyl, or dione oxidation levels.二烯与邻位二氧代烃的连续 C-C 偶联：钌催化的[4+2]环加成跨越二醇、羟羰基或二酮氧化水平。
J Am Chem Soc. 2013 Mar 13;135(10):3796-9. doi: 10.1021/ja400691t. Epub 2013 Feb 28.
3
Formation of C-C bonds via ruthenium-catalyzed transfer hydrogenation().通过钌催化的转移氢化反应形成碳-碳键（）。
Pure Appl Chem. 2012;84(8):1729-1739. doi: 10.1351/PAC-CON-11-10-18. Epub 2012 Mar 13.
4
Application of ruthenium complexes of triazole-containing tridentate ligands to asymmetric transfer hydrogenation of ketones.含三唑的三齿配体钌配合物在酮的不对称转移氢化中的应用。
Org Lett. 2012 Oct 19;14(20):5230-3. doi: 10.1021/ol302354z. Epub 2012 Oct 1.
5
Direct, redox-neutral prenylation and geranylation of secondary carbinol C-H bonds: C4-regioselectivity in ruthenium-catalyzed C-C couplings of dienes to α-hydroxy esters.直接、氧化还原中性的仲碳醇 C-H 键的香叶基化和法呢基化：二烯与 α-羟基酯的钌催化 C-C 偶联中 C4-区域选择性。
J Am Chem Soc. 2012 Sep 26;134(38):15700-3. doi: 10.1021/ja3075049. Epub 2012 Sep 17.
6
Enantioselective copper-catalyzed reductive coupling of alkenylazaarenes with ketones.手性铜催化烯基氮杂芳烃与酮的还原偶联反应。
J Am Chem Soc. 2012 May 23;134(20):8428-31. doi: 10.1021/ja3036916. Epub 2012 May 11.
7
Unlocking Hydrogenation for C-C Bond Formation: A Brief Overview of Enantioselective Methods.解锁用于碳-碳键形成的氢化反应：对映选择性方法概述
Org Process Res Dev. 2011 Nov 18;15(6):1236-1242. doi: 10.1021/op200195m.
8
Synthesis of α-amino acid amides: ruthenium-catalyzed amination of α-hydroxy amides.α-氨基酸酰胺的合成：钌催化α-羟基酰胺的胺化反应。
Angew Chem Int Ed Engl. 2011 Nov 18;50(47):11197-201. doi: 10.1002/anie.201104309. Epub 2011 Oct 10.
9
Recent advances in the transition metal-catalyzed twofold oxidative C-H bond activation strategy for C-C and C-N bond formation.过渡金属催化的双重氧化 C-H 键活化策略在 C-C 和 C-N 键形成中的最新进展。
Chem Soc Rev. 2011 Oct;40(10):5068-83. doi: 10.1039/c1cs15082k. Epub 2011 Jun 6.
10
Enantioselective rhodium-catalyzed addition of arylboronic acids to alkenylheteroarenes.手性铑催化芳基硼酸对烯基杂芳烃的加成反应。
J Am Chem Soc. 2010 Oct 20;132(41):14373-5. doi: 10.1021/ja106809p.
Zotero 插件