钌催化通过转移氢化形成碳-碳键：丙二烯与多聚甲醛及高级醛的支链选择性还原偶联反应。
Ruthenium catalyzed C-C bond formation via transfer hydrogenation: branch-selective reductive coupling of allenes to paraformaldehyde and higher aldehydes.
作者信息
Ngai Ming-Yu, Skucas Eduardas, Krische Michael J
机构信息
University of Texas at Austin, Department of Chemistry and Biochemistry, Austin, Texas 78712, USA.
出版信息
Org Lett. 2008 Jul 3;10(13):2705-8. doi: 10.1021/ol800836v. Epub 2008 Jun 6.
Abstract
Under the conditions of ruthenium-catalyzed transfer hydrogenation employing 2-propanol as the terminal reductant, 1,1-disubstituted allenes 1a- h engage in reductive coupling to paraformaldehyde to furnish homoallylic alcohols 2a- h. Under identical transfer hydrogenation conditions, 1,1-disubstituted allenes engage in reductive coupling to aldehydes 3a- f to furnish homoallylic alcohols 4a- n. In all cases, reductive coupling occurs with branched regioselectivity to deliver homoallylic alcohols bearing all-carbon quaternary centers.
摘要
在以2-丙醇作为末端还原剂的钌催化转移氢化条件下，1,1-二取代丙二烯1a - h与多聚甲醛进行还原偶联反应，生成高烯丙醇2a - h。在相同的转移氢化条件下，1,1-二取代丙二烯与醛3a - f进行还原偶联反应，生成高烯丙醇4a - n。在所有情况下，还原偶联反应均以支链区域选择性进行，生成带有全碳季碳中心的高烯丙醇。
相似文献
1
Ruthenium catalyzed C-C bond formation via transfer hydrogenation: branch-selective reductive coupling of allenes to paraformaldehyde and higher aldehydes.钌催化通过转移氢化形成碳-碳键：丙二烯与多聚甲醛及高级醛的支链选择性还原偶联反应。
Org Lett. 2008 Jul 3;10(13):2705-8. doi: 10.1021/ol800836v. Epub 2008 Jun 6.
2
Diene hydroacylation from the alcohol or aldehyde oxidation level via ruthenium-catalyzed C-C bond-forming transfer hydrogenation: synthesis of beta,gamma-unsaturated ketones.通过钌催化的形成碳-碳键的转移氢化反应，从醇或醛氧化水平进行二烯氢酰化反应：β,γ-不饱和酮的合成。
J Am Chem Soc. 2008 Oct 29;130(43):14120-2. doi: 10.1021/ja805356j. Epub 2008 Oct 8.
3
Ruthenium-catalyzed C-C coupling of fluorinated alcohols with allenes: dehydrogenation at the energetic limit of β-hydride elimination.钌催化氟化醇与丙二烯的碳-碳偶联：在β-氢消除的能量极限下的脱氢反应。
Angew Chem Int Ed Engl. 2015 Apr 27;54(18):5465-9. doi: 10.1002/anie.201500238. Epub 2015 Mar 10.
4
anti-Aminoallylation of aldehydes via ruthenium-catalyzed transfer hydrogenative coupling of sulfonamido allenes: 1,2-aminoalcohols.通过钌催化的磺酰胺基丙二烯转移氢化偶联实现醛的抗氨甲酰化反应：1,2-氨基醇
J Am Chem Soc. 2009 Apr 15;131(14):5054-5. doi: 10.1021/ja900827p.
5
Amplification of anti-diastereoselectivity via Curtin-Hammett effects in ruthenium-catalyzed hydrohydroxyalkylation of 1,1-disubstituted allenes: diastereoselective formation of all-carbon quaternary centers.通过 Curtin-Hammett 效应增强钌催化 1,1-二取代丙二烯的氢氢羟烷基化反应的非对映选择性：全碳季碳中心的非对映选择性形成。
J Am Chem Soc. 2011 Feb 2;133(4):1141-4. doi: 10.1021/ja1104156. Epub 2010 Dec 22.
6
Ruthenium-catalyzed C-C bond forming transfer hydrogenation: carbonyl allylation from the alcohol or aldehyde oxidation level employing acyclic 1,3-dienes as surrogates to preformed allyl metal reagents.钌催化的碳-碳键形成转移氢化反应：以无环1,3-二烯作为预制烯丙基金属试剂的替代物，从醇或醛氧化态进行羰基烯丙基化反应。
J Am Chem Soc. 2008 May 21;130(20):6338-9. doi: 10.1021/ja801213x. Epub 2008 Apr 29.
7
Direct ruthenium-catalyzed C-C coupling of ethanol: diene hydro-hydroxyethylation to form all-carbon quaternary centers.直接钌催化的乙醇 C-C 偶联反应：二烯的氢-羟乙基化反应形成全碳季碳原子。
Org Lett. 2010 Jun 18;12(12):2844-6. doi: 10.1021/ol101077v.
8
Direct vinylation of alcohols or aldehydes employing alkynes as vinyl donors: a ruthenium catalyzed C-C bond-forming transfer hydrogenation.以炔烃作为乙烯基供体实现醇或醛的直接乙烯基化：钌催化的碳-碳键形成转移氢化反应
J Am Chem Soc. 2009 Feb 18;131(6):2066-7. doi: 10.1021/ja809456u.
9
Regioselective Hydrohydroxyalkylation of Styrene with Primary Alcohols or Aldehydes via Ruthenium-Catalyzed C-C Bond Forming Transfer Hydrogenation.通过钌催化的 C-C 键形成转移氢化反应实现苯乙烯与伯醇或醛的区域选择性氢羟烷基化。
Angew Chem Int Ed Engl. 2016 Dec 23;55(52):16119-16122. doi: 10.1002/anie.201609056. Epub 2016 Dec 2.
10
Alkyne-aldehyde reductive C-C coupling through ruthenium-catalyzed transfer hydrogenation: direct regio- and stereoselective carbonyl vinylation to form trisubstituted allylic alcohols in the absence of premetallated reagents.通过钌催化转移氢化实现炔醛的还原 C-C 偶联：在不存在预金属化试剂的情况下，通过直接区域和立体选择性羰基乙烯化形成三取代烯丙醇。
Chemistry. 2011 Oct 24;17(44):12437-43. doi: 10.1002/chem.201101554. Epub 2011 Sep 27.
引用本文的文献
1
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.
2
Iridium-, Ruthenium-, and Nickel-Catalyzed C-C Couplings of Methanol, Formaldehyde, and Ethanol with π-Unsaturated Pronucleophiles via Hydrogen Transfer.铱、钌和镍催化甲醇、甲醛和乙醇与π-不饱和给电子体通过氢转移的 C-C 偶联反应。
J Org Chem. 2023 Apr 21;88(8):4965-4974. doi: 10.1021/acs.joc.2c02356. Epub 2022 Nov 30.
3
Concise synthesis of -thiomethyl benzoimidazoles through base-promoted sequential multicomponent assembly.通过碱促进的顺序多组分组装简洁合成硫代甲基苯并咪唑。
RSC Adv. 2019 Sep 26;9(52):30570-30574. doi: 10.1039/c9ra06144d. eCollection 2019 Sep 23.
4
Copper-catalyzed hydroformylation and hydroxymethylation of styrenes.铜催化的苯乙烯氢甲酰化和羟甲基化反应
Chem Sci. 2021 Oct 29;12(44):14937-14943. doi: 10.1039/d1sc05474k. eCollection 2021 Nov 17.
5
Understanding Halide Counterion Effects in Enantioselective Ruthenium-Catalyzed Carbonyl (α-Aryl)allylation: Alkynes as Latent Allenes and Trifluoroethanol-Enhanced Turnover in The Conversion of Ethanol to Higher Alcohols via Hydrogen Auto-transfer.理解卤化物抗衡离子在对映选择性钌催化羰基（α-芳基）烯丙基化反应中的作用：炔烃作为潜伏的烯丙基化合物，以及三氟乙醇在氢自动转移转化乙醇为更高醇中的增强转化。
J Am Chem Soc. 2021 Oct 13;143(40):16709-16717. doi: 10.1021/jacs.1c07857. Epub 2021 Oct 4.
6
Allenes and Dienes as Chiral Allylmetal Pronucleophiles in Catalytic Enantioselective C=X Addition: Historical Perspective and State-of-The-Art Survey.烯丙基试剂和二烯作为手性烯丙基金属亲核试剂在催化对映选择性 C=X 加成反应中的应用：历史透视和最新进展综述。
Chemistry. 2021 Sep 15;27(52):13107-13116. doi: 10.1002/chem.202101890. Epub 2021 Jul 29.
7
Enantioselective Ruthenium-BINAP-Catalyzed Carbonyl Reductive Coupling of Alkoxyallenes: Convergent Construction of -Diols via ()-σ-Allylmetal Intermediates.手性钌-BINAP 催化的烷氧基丙二烯的羰基还原偶联反应：通过 ()-σ-烯丙基金属中间体构建 -二醇的会聚合成。
J Am Chem Soc. 2021 Jun 16;143(23):8849-8854. doi: 10.1021/jacs.1c03480. Epub 2021 Jun 1.
8
Diastereo-, Enantio-, and Selective Formation of Secondary Alcohol and Quaternary Carbon Stereocenters by Cu-Catalyzed Additions of B-Substituted Allyl Nucleophiles to Carbonyls.铜催化的 B-取代烯丙基亲核试剂与羰基的加成反应，实现了立体选择性、对映选择性和二级醇及季碳立体中心的形成。
Org Lett. 2020 Dec 4;22(23):9269-9275. doi: 10.1021/acs.orglett.0c03495. Epub 2020 Nov 18.
9
Inversion of Enantioselectivity in Allene Gas versus Allyl Acetate Reductive Aldehyde Allylation Guided by Metal-Centered Stereogenicity: An Experimental and Computational Study.以金属中心手性为导向的丙二烯气体与乙酸烯丙酯还原醛烯丙基化反应中对映选择性的反转：一项实验与计算研究
ACS Catal. 2019 Oct 4;9(10):9158-9163. doi: 10.1021/acscatal.9b03695. Epub 2019 Sep 11.
10
Engaging Aldehydes in CuH-Catalyzed Reductive Coupling Reactions: Stereoselective Allylation with Unactivated 1,3-Diene Pronucleophiles.铜氢催化还原偶联反应中醛的参与：非活化 1,3-二烯给体亲核试剂的立体选择性烯丙基化反应。
Angew Chem Int Ed Engl. 2019 Nov 18;58(47):17074-17080. doi: 10.1002/anie.201911008. Epub 2019 Oct 22.
本文引用的文献
1
Carbonyl propargylation from the alcohol or aldehyde oxidation level employing 1,3-enynes as surrogates to preformed allenylmetal reagents: a ruthenium-catalyzed C-C bond-forming transfer hydrogenation.使用1,3-烯炔作为预制联烯基金属试剂的替代物，从醇或醛氧化水平进行羰基炔丙基化反应：一种钌催化的碳-碳键形成转移氢化反应。
Angew Chem Int Ed Engl. 2008;47(28):5220-3. doi: 10.1002/anie.200801359.
2
Ruthenium-catalyzed C-C bond forming transfer hydrogenation: carbonyl allylation from the alcohol or aldehyde oxidation level employing acyclic 1,3-dienes as surrogates to preformed allyl metal reagents.钌催化的碳-碳键形成转移氢化反应：以无环1,3-二烯作为预制烯丙基金属试剂的替代物，从醇或醛氧化态进行羰基烯丙基化反应。
J Am Chem Soc. 2008 May 21;130(20):6338-9. doi: 10.1021/ja801213x. Epub 2008 Apr 29.
3
Diastereo- and enantioselective hydrogenative aldol coupling of vinyl ketones: design of effective monodentate TADDOL-like phosphonite ligands.乙烯基酮的非对映和对映选择性氢化羟醛偶联反应：高效单齿类TADDOL亚磷酸酯配体的设计
J Am Chem Soc. 2008 Mar 5;130(9):2746-7. doi: 10.1021/ja710862u. Epub 2008 Feb 12.
4
Iridium-catalyzed C-C coupling via transfer hydrogenation: carbonyl addition from the alcohol or aldehyde oxidation level employing 1,3-cyclohexadiene.铱催化通过转移氢化进行的碳-碳偶联：利用1,3-环己二烯从醇或醛氧化水平进行羰基加成
Org Lett. 2008 Mar 6;10(5):1033-5. doi: 10.1021/ol800159w. Epub 2008 Feb 7.
5
Catalytic C-C coupling via transfer hydrogenation: reverse prenylation, crotylation, and allylation from the alcohol or aldehyde oxidation level.通过转移氢化实现催化碳-碳偶联：从醇或醛氧化水平进行反向异戊烯基化、巴豆酰化和烯丙基化。
J Am Chem Soc. 2007 Dec 12;129(49):15134-5. doi: 10.1021/ja077389b. Epub 2007 Nov 17.
6
Asymmetric transfer hydrogenation of ketones with bifunctional transition metal-based molecular catalysts.双功能过渡金属基分子催化剂用于酮的不对称转移氢化反应。
Acc Chem Res. 2007 Dec;40(12):1300-8. doi: 10.1021/ar700134q. Epub 2007 Oct 26.
7
Enantioselective iridium-catalyzed imine vinylation: optically enriched allylic amines via alkyne-imine reductive coupling mediated by hydrogen.对映选择性铱催化的亚胺乙烯基化反应：通过氢气介导的炔烃-亚胺还原偶联反应制备光学富集的烯丙基胺。
J Am Chem Soc. 2007 Oct 24;129(42):12644-5. doi: 10.1021/ja075438e. Epub 2007 Oct 3.
8
Carbonyl allylation in the absence of preformed allyl metal reagents: reverse prenylation via iridium-catalyzed hydrogenative coupling of dimethylallene.在不存在预先形成的烯丙基金属试剂的情况下进行羰基烯丙基化反应：通过铱催化的二甲基丙二烯氢化偶联实现逆异戊烯基化反应。
J Am Chem Soc. 2007 Oct 24;129(42):12678-9. doi: 10.1021/ja075971u. Epub 2007 Sep 27.
9
Enantiomerically enriched allylic alcohols and allylic amines via C-C bond-forming hydrogenation: asymmetric carbonyl and imine vinylation.通过形成碳 - 碳键的氢化反应制备对映体富集的烯丙醇和烯丙胺：不对称羰基和亚胺乙烯基化反应
Acc Chem Res. 2007 Dec;40(12):1394-401. doi: 10.1021/ar7001123. Epub 2007 Sep 5.
10
Rhodium-catalyzed reductive mannich coupling of vinyl ketones to N-sulfonylimines mediated by hydrogen.铑催化的乙烯基酮与N-磺酰亚胺的还原曼尼希偶联反应，由氢气介导。
J Org Chem. 2007 Jul 20;72(15):5843-6. doi: 10.1021/jo070779w. Epub 2007 Jun 21.
Zotero 插件