Dft study on the mechanism of tandem oxidative acetoxylation/ortho c-h activation/carbocyclization catalyzed by pd(oac)(2)
文献类型：期刊论文
| 作者 | Li, Hui1,2; Ma, Xuelu1,3,4; Zhang, Baohua5; Lei, Ming1 |
| 刊名 | Organometallics
 |
| 出版日期 | 2016-10-10 |
| 卷号 | 35期号:19页码:3301-3310 |
| ISSN号 | 0276-7333 |
| DOI | 10.1021/acs.organomet.6b00503 |
| 通讯作者 | Lei, ming(leim@mail.buct.edu.cn) |
| 英文摘要 | A density functional theory (dft) study has been conducted to unveil the mechanisms of tandem oxidative acetoxylation/ortho c-h activation/carbocyclization catalyzed by pd(oac)(2). the potential competitive reaction pathways between oxidative acetoxylation and ortho c-h activation, c-h activation with outer-sphere and inner-sphere acetate ligands, and the role of dmso in the reaction have been discussed in detail. the calculated results indicate that the oxidative acetoxylation proceeds before ortho c-h activation in this tandem reaction in a neutral system without dmso as a ligand coordinated to pd. a six-membered transition state is proposed in the oxidative acetoxylation step, and a six-membered transition state is proposed in the palladium carboxylate catalyzed sp(2) c-h activation step. the coordination of outer-sphere acetate ion to pd decreases the energy barrier of the step of ortho sp(2) c-h activation. in addition, this theoretical work demonstrates that the cosolvent dmso as a ligand coordinated with pd decreases the energy barrier of c-h activation. also, the reaction tandem sequence changes to ortho c-h activation/oxidative acetoxylation/carbocyclization induced by dmso as a ligand coordinated with pd. |
| WOS关键词 | EFFECTIVE CORE POTENTIALS ; SUBSTITUTED CONJUGATED DIENES ; CARBON BOND FORMATION ; MOLECULAR CALCULATIONS ; ARYLATING CARBOCYCLIZATION ; C(SP(3))-H ACTIVATION ; PALLADIUM ; FUNCTIONALIZATION ; COMPLEXES ; POLYMERIZATION |
| WOS研究方向 | Chemistry |
| WOS类目 | Chemistry, Inorganic & Nuclear ; Chemistry, Organic |
| 语种 | 英语 |
| WOS记录号 | WOS:000385209400008 |
| 出版者 | AMER CHEMICAL SOC |
| URI标识 | http://www.irgrid.ac.cn/handle/1471x/2374199 |
| 专题 | 计算机网络信息中心 |
| 通讯作者 | Lei, Ming |
| 作者单位 | 1.Beijing Univ Chem Technol, Coll Sci, Inst Mat Med, State Key Lab Chem Resource Engn, Beijing 100029, Peoples R China 2.Beifang Univ Nationalities, Coll Chem & Chem Engn, Ningxia 750021, Peoples R China 3.Tsinghua Univ, Minist Educ, Dept Chem, Beijing 100084, Peoples R China 4.Tsinghua Univ, Minist Educ, Key Lab Organ Optoelect & Mol Engn, Beijing 100084, Peoples R China 5.Chinese Acad Sci, Supercomp Ctr, Comp Network Informat Ctr, Beijing 100190, Peoples R China |
| 推荐引用方式 GB/T 7714 | Li, Hui,Ma, Xuelu,Zhang, Baohua,et al. Dft study on the mechanism of tandem oxidative acetoxylation/ortho c-h activation/carbocyclization catalyzed by pd(oac)(2)[J]. Organometallics,2016,35(19):3301-3310. |
| APA | Li, Hui,Ma, Xuelu,Zhang, Baohua,&Lei, Ming.(2016).Dft study on the mechanism of tandem oxidative acetoxylation/ortho c-h activation/carbocyclization catalyzed by pd(oac)(2).Organometallics,35(19),3301-3310. |
| MLA | Li, Hui,et al."Dft study on the mechanism of tandem oxidative acetoxylation/ortho c-h activation/carbocyclization catalyzed by pd(oac)(2)".Organometallics 35.19(2016):3301-3310. |
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