通过有氧氧化 Heck 反应合成支化共轭二烯中的催化剂控制区域选择性。
Catalyst-controlled regioselectivity in the synthesis of branched conjugated dienes via aerobic oxidative Heck reactions.
机构信息
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.
出版信息
J Am Chem Soc. 2012 Oct 10;134(40):16496-9. doi: 10.1021/ja307371w. Epub 2012 Sep 28.
Abstract
Pd-catalyzed aerobic oxidative coupling of vinylboronic acids and electronically unbiased alkyl olefins provides regioselective access to 1,3-disubstituted conjugated dienes. Catalyst-controlled regioselectivity is achieved by using 2,9-dimethylphenanthroline as a ligand. The observed regioselectivity is opposite to that observed from a traditional (nonoxidative) Heck reaction between a vinyl bromide and an alkene. DFT computational studies reveal that steric effects of the 2,9-dimethylphenanthroline ligand promote C-C bond formation at the internal position of the alkene.
摘要
钯催化的乙烯基硼酸和非电子偏向性的烷基烯烃的有氧氧化偶联反应为 1,3-二取代共轭二烯提供了区域选择性的合成途径。通过使用 2,9-二甲基菲咯啉作为配体，可以实现催化剂控制的区域选择性。观察到的区域选择性与传统（非氧化） Heck 反应中乙烯基溴化物和烯烃之间的反应相反。DFT 计算研究表明，2,9-二甲基菲咯啉配体的空间位阻效应促进了烯烃内部位置的 C-C 键形成。
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本文引用的文献
1
Intermolecular Mizoroki-Heck reaction of aliphatic olefins with high selectivity for substitution at the internal position.脂肪族烯烃的分子间 Mizoroki-Heck 反应，对内位取代具有高选择性。
Angew Chem Int Ed Engl. 2012 Jun 11;51(24):5915-9. doi: 10.1002/anie.201201806. Epub 2012 May 3.
2
Nickel-catalyzed Heck-type reactions of benzyl chlorides and simple olefins.镍催化的苄基氯和简单烯烃的 Heck 型反应。
J Am Chem Soc. 2011 Nov 30;133(47):19020-3. doi: 10.1021/ja209235d. Epub 2011 Nov 8.
3
Regiocontrolled aerobic oxidative coupling of indoles and benzene using Pd catalysts with 4,5-diazafluorene ligands.使用带有 4,5-二氮菲配体的钯催化剂进行吲哚和苯的区域控制有氧氧化偶联。
Chem Commun (Camb). 2011 Oct 7;47(37):10257-9. doi: 10.1039/c1cc13632a. Epub 2011 Aug 22.
4
Highly selective synthesis of conjugated dienoic and trienoic esters via alkyne elementometalation-Pd-catalyzed cross-coupling.通过炔基金属化-Pd 催化交叉偶联反应高选择性合成共轭二烯酸酯和三烯酸酯。
Proc Natl Acad Sci U S A. 2011 Jul 12;108(28):11344-9. doi: 10.1073/pnas.1105155108. Epub 2011 Jun 27.
5
The asymmetric Heck and related reactions.不对称 Heck 反应及相关反应。
Chem Soc Rev. 2011 Oct;40(10):5122-50. doi: 10.1039/c1cs15101k. Epub 2011 Jun 15.
6
Operationally simple and highly (E)-styrenyl-selective Heck reactions of electronically nonbiased olefins.操作简单且高（E）-烯丙基选择性 Heck 反应的电子非偏见烯烃。
J Am Chem Soc. 2011 Jun 29;133(25):9692-5. doi: 10.1021/ja203164p. Epub 2011 Jun 6.
7
From α-arylation of olefins to acylation with aldehydes: a journey in regiocontrol of the Heck reaction.从烯烃的α-芳基化到与醛的酰化：Heck 反应区域控制的历程。
Acc Chem Res. 2011 Aug 16;44(8):614-26. doi: 10.1021/ar200053d. Epub 2011 May 25.
8
Pd-diimine: a highly selective catalyst system for the base-free oxidative Heck reaction.钯-二亚胺：一种用于无碱氧化 Heck 反应的高选择性催化剂体系。
J Org Chem. 2011 May 6;76(9):3498-501. doi: 10.1021/jo101942f. Epub 2011 Mar 23.
9
Aerobic Oxidative Coupling of o-Xylene: Discovery of 2-Fluoropyridine as a Ligand to Support Selective Pd-Catalyzed C-H Functionalization.邻二甲苯的有氧氧化偶联反应：发现2-氟吡啶作为配体用于支持选择性钯催化的C-H官能团化反应
Adv Synth Catal. 2010 Dec 17;352(18):3223-3229. doi: 10.1002/adsc.201000771.
10
Allylic C-H acetoxylation with a 4,5-diazafluorenone-ligated palladium catalyst: a ligand-based strategy to achieve aerobic catalytic turnover.钯催化烯丙位 C-H 乙酰化反应：一种基于配体的策略实现有氧催化循环。
J Am Chem Soc. 2010 Nov 3;132(43):15116-9. doi: 10.1021/ja105829t.
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