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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。

Ruthenium-catalyzed C-C coupling of fluorinated alcohols with allenes: dehydrogenation at the energetic limit of β-hydride elimination.

作者信息

Sam Brannon, Luong Tom, Krische Michael J

机构信息

University of Texas at Austin, Department of Chemistry, 105 E 24th St. (A5300), Austin, TX 78712-1167 (USA).

出版信息

Angew Chem Int Ed Engl. 2015 Apr 27;54(18):5465-9. doi: 10.1002/anie.201500238. Epub 2015 Mar 10.

DOI:10.1002/anie.201500238
PMID:25757459
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC4405479/
Abstract

Ruthenium(II) complexes catalyze the CC coupling of 1,1-disubstituted allenes and fluorinated alcohols to form homoallylic alcohols bearing all-carbon quaternary centers with good to complete levels of diastereoselectivity. Whereas fluorinated alcohols are relatively abundant and tractable, the corresponding aldehydes are often not commercially available because of their instability.

摘要

钌（II）配合物催化1,1-二取代丙二烯与氟化醇的碳-碳偶联反应，以形成具有全碳季碳中心的高烯丙醇，非对映选择性良好至完全。虽然氟化醇相对丰富且易于处理，但相应的醛由于其不稳定性，通常无法从商业途径获得。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2f7f/4405479/9559cf2c11eb/nihms-675897-f0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2f7f/4405479/02a171ac47f2/nihms-675897-f0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2f7f/4405479/544bbbb140a3/nihms-675897-f0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2f7f/4405479/75a5fbea316d/nihms-675897-f0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2f7f/4405479/9559cf2c11eb/nihms-675897-f0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2f7f/4405479/02a171ac47f2/nihms-675897-f0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2f7f/4405479/544bbbb140a3/nihms-675897-f0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2f7f/4405479/75a5fbea316d/nihms-675897-f0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2f7f/4405479/9559cf2c11eb/nihms-675897-f0007.jpg

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本文引用的文献

1
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Angew Chem Int Ed Engl. 2014 Aug 25;53(35):9142-50. doi: 10.1002/anie.201403873. Epub 2014 Jul 23.
2
Fluorine in pharmaceutical industry: fluorine-containing drugs introduced to the market in the last decade (2001-2011).制药行业中的氟：过去十年（2001 - 2011年）推向市场的含氟药物
Chem Rev. 2014 Feb 26;114(4):2432-506. doi: 10.1021/cr4002879. Epub 2013 Dec 3.
3
Introduction of fluorine and fluorine-containing functional groups.
Asymmetric Ruthenium-Catalyzed Carbonyl Allylations by Gaseous Allene via Hydrogen Auto-Transfer: 1° vs 2° Alcohol Dehydrogenation for Streamlined Polyketide Construction.
通过氢自动转移实现气态丙二烯不对称钌催化的羰基烯丙基化反应：用于简化聚酮化合物构建的一级醇与二级醇脱氢反应
ACS Catal. 2023 Feb 3;13(3):1662-1668. doi: 10.1021/acscatal.2c05425. Epub 2023 Jan 12.
4
Ruthenium-Catalyzed Butadiene-Mediated Crotylation and Oxazaborolidine-Catalyzed Vinylogous Mukaiyama Aldol Reaction for The Synthesis of C1-C19 and C23-C35 of Neaumycin B.钌催化丁二烯介导的烯丙基化和恶唑硼烷催化的 vinylogous Mukaiyama 缩醛反应在 Neaumycin B 的 C1-C19 和 C23-C35 的合成中的应用。
Angew Chem Int Ed Engl. 2022 Dec 23;61(52):e202214786. doi: 10.1002/anie.202214786. Epub 2022 Nov 23.
5
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J Am Chem Soc. 2022 May 18;144(19):8861-8869. doi: 10.1021/jacs.2c03614. Epub 2022 May 3.
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Chemistry. 2021 Sep 15;27(52):13107-13116. doi: 10.1002/chem.202101890. Epub 2021 Jul 29.
8
Synthesis of Homoallylic Alcohols with Acyclic Quaternary Centers through Co -Catalyzed Three-Component C-H Bond Addition to Internally Substituted Dienes and Carbonyls.通过共催化三组分 C-H 键加成到内部取代的二烯和羰基化合物来合成具有非环状季碳原子的偕丙醇。
Angew Chem Int Ed Engl. 2019 Sep 2;58(36):12590-12594. doi: 10.1002/anie.201906633. Epub 2019 Aug 1.
9
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5
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8
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J Am Chem Soc. 2011 Aug 17;133(32):12795-800. doi: 10.1021/ja204570w. Epub 2011 Jul 25.
9
Iridium-catalysed direct C-C coupling of methanol and allenes.铱催化甲醇与丙二烯的直接 C-C 偶联反应。
Nat Chem. 2011 Apr;3(4):287-90. doi: 10.1038/nchem.1001. Epub 2011 Feb 27.
10
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.