空间位阻使具有挑战性的C(sp3)-F还原消除反应成为可能。
Steric Crowding Makes Challenging C(sp3)-F Reductive Eliminations Feasible.
作者信息
Zhao Shu-Bin, Becker Jennifer J, Gagné Michel R
机构信息
Caudill Laboratories, Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290, USA.
出版信息
Organometallics. 2011 Aug 8;30(15):3926-3929. doi: 10.1021/om200515f.
Abstract
A high-yielding fluorination of (triphos)Pt-R(+) has been achieved using an array of F(+) sources, with XeF(2) yielding R-F in minutes. The C-F coupling proved to be a stereoretentive process that proceeds via a concerted reductive elimination from a putative dicationic Pt(IV) center. The larger the steric congestion of the (triphos)Pt-C(sp3) (+) complexes, the more efficient the fluorination, seemingly a result of sterically accelerated C-F reductive elimination along with simultaneous deceleration of its competing processes (β-H elimination).
摘要
使用一系列F(+)源实现了(triphos)Pt-R(+)的高产率氟化反应，其中XeF(2)在数分钟内即可生成R-F。C-F偶联反应被证明是一个立体保持过程，它通过从假定的二价铂(IV)中心协同还原消除来进行。(triphos)Pt-C(sp3)(+)配合物的空间位阻越大，氟化反应效率越高，这似乎是空间加速C-F还原消除以及同时减缓其竞争过程（β-H消除）的结果。
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本文引用的文献
1
Catalysis for fluorination and trifluoromethylation.氟化和三氟甲基化反应的催化。
Nature. 2011 May 26;473(7348):470-7. doi: 10.1038/nature10108.
2
Terminating platinum-initiated cation-olefin reactions with simple alkenes.用简单烯烃终止铂引发的阳离子-烯烃反应。
Angew Chem Int Ed Engl. 2011 Jun 14;50(25):5658-61. doi: 10.1002/anie.201100463. Epub 2011 May 13.
3
Palladium-catalyzed allylic fluorination.钯催化的烯丙基氟化反应。
Angew Chem Int Ed Engl. 2011 Mar 7;50(11):2613-7. doi: 10.1002/anie.201007307. Epub 2011 Feb 8.
4
Bystanding F+ oxidants enable selective reductive elimination from high-valent metal centers in catalysis.旁观的 F+ 氧化剂能够在催化中使高价金属中心发生选择性还原消除。
Angew Chem Int Ed Engl. 2011 Feb 11;50(7):1478-91. doi: 10.1002/anie.201005142. Epub 2011 Jan 24.
5
Palladium-catalyzed tandem fluorination and cyclization of enynes.钯催化的烯炔的串联氟化和环化反应。
Org Lett. 2011 Feb 18;13(4):772-5. doi: 10.1021/ol103039x. Epub 2011 Jan 20.
6
Palladium-catalyzed asymmetric synthesis of allylic fluorides.钯催化的烯丙基氟化物的不对称合成。
J Am Chem Soc. 2010 Dec 15;132(49):17402-4. doi: 10.1021/ja109120n. Epub 2010 Nov 18.
7
Fluorine-enabled cationic gold catalysis: functionalized hydration of alkynes.
Angew Chem Int Ed Engl. 2010 Sep 24;49(40):7247-52. doi: 10.1002/anie.201003593.
8
Palladium-catalyzed alkoxyamination of alkenes with use of N-fluorobenzenesulfonimide as oxidant.钯催化的烯与 N-氟代苯磺酰胺作为氧化剂的烷氧基化反应。
J Org Chem. 2010 Sep 17;75(18):6294-6. doi: 10.1021/jo101171g.
9
Silver-catalyzed late-stage fluorination.银催化的晚期氟化反应。
J Am Chem Soc. 2010 Sep 1;132(34):12150-4. doi: 10.1021/ja105834t.
10
Reagent-dependent formation of C-C and C-F bonds in Pt complexes: an unexpected twist in the electrophilic fluorination chemistry.Pt 配合物中 C-C 和 C-F 键的试剂依赖性形成：亲电氟化化学中的一个意外转折。
J Am Chem Soc. 2010 Aug 11;132(31):10626-7. doi: 10.1021/ja101436w.
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