ISL OpenIR  > 青海盐湖研究所知识仓储
Computation-Guided Development of Au-Catalyzed Cycloisomerizations Proceeding via 1,2-Si or 1,2-H Migrations: Regiodivergent Synthesis of Silylfurans
Dudnik, Alexander S.2; Xia, Yuanzhi1,3; Li, Yahong1,3; Gevorgyan, Vladimir2
2010-06-09
发表期刊JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷号132期号:22页码:7645-7655
文章类型Article
摘要A novel highly efficient regiodivergent Au-catalyzed cycloisomerization of allenyl and homopropargylic ketones into synthetically valuable 2- and 3-silylfurans has been designed with the aid of DFT calculations. This cascade transformation features 1,2-Si or 1,2-H migrations in a common Au-carbene intermediate. Both experimental and computational results clearly indicate that the 1,2-Si migration is kinetically favored over the 1,2-shifts of H, alkyl, and aryl groups in the beta-Si-substituted Au-carbenes. In addition, experimental results on the Au(I)-catalyzed cycloisomerization of homopropargylic ketones demonstrated that counterion and solvent effects could reverse the above migratory preference. The DFT calculations provided a rationale for this 1,2-migration regiodivergency. Thus, in the case of Ph(3)PAuSbF(6), DFT-simulated reaction proceeds through the initial propargyl-allenyl isomerization followed by the cyclization into the Au-carbene intermediate with the exclusive formation of 1,2-Si migration products and solvent effects cannot affect this regioselectivity. However, in the case of a TfO(-) counterion, reaction occurs via the initial 5-endo-dig cyclization to give a cyclic furyl-Au intermediate. In the case of nonpolar solvents, subsequent ipso-protiodeauration of the latter is kinetically more favorable than the generation of the common Au-carbene intermediate and leads to the formation of formal 1,2-H migration products. In contrast, when polar solvent is employed in this DFT-simulated reaction, beta-to-Au protonation of the furyl-Au species to give a Au-carbene intermediate competes with the ipso-protiodeauration. Subsequent dissociation of the triflate ligand in this carbene in polar media due to efficient solvation of charged intermediates facilitates formation of the 1,2-Si shift products. The above results of the DFT calculations were validated by the experimental data. The present study demonstrates that DFT calculations could efficiently support experimental results, providing guidance for rational design of new catalytic transformations.
WOS标题词Science & Technology ; Physical Sciences
关键词[WOS]HOMOGENEOUS GOLD CATALYSIS ; HIGHLY SUBSTITUTED FURANS ; EFFICIENT SYNTHESIS ; POLYSUBSTITUTED FURANS ; TETRASUBSTITUTED FURANS ; 2,5-DISUBSTITUTED FURANS ; CASCADE REACTIONS ; ALLENYL SULFIDES ; PI-ACIDS ; HETEROCYCLES
收录类别SCI ; IC ; CCR
语种英语
WOS研究方向Chemistry
WOS类目Chemistry, Multidisciplinary
WOS记录号WOS:000278837100023
引用统计
文献类型期刊论文
条目标识符http://ir.isl.ac.cn/handle/363002/5954
专题青海盐湖研究所知识仓储
作者单位1.Suzhou Univ, Key Lab Organ Synth Jiangsu Prov, Dept Chem & Chem Engn, Suzhou 215006, Peoples R China
2.Univ Illinois, Dept Chem, Chicago, IL 60607 USA
3.Chinese Acad Sci, Key Lab Salt Lake Resources & Chem, Qinghai Inst Salt Lakes, Xining 810008, Peoples R China
推荐引用方式
GB/T 7714
Dudnik, Alexander S.,Xia, Yuanzhi,Li, Yahong,et al. Computation-Guided Development of Au-Catalyzed Cycloisomerizations Proceeding via 1,2-Si or 1,2-H Migrations: Regiodivergent Synthesis of Silylfurans[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2010,132(22):7645-7655.
APA Dudnik, Alexander S.,Xia, Yuanzhi,Li, Yahong,&Gevorgyan, Vladimir.(2010).Computation-Guided Development of Au-Catalyzed Cycloisomerizations Proceeding via 1,2-Si or 1,2-H Migrations: Regiodivergent Synthesis of Silylfurans.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,132(22),7645-7655.
MLA Dudnik, Alexander S.,et al."Computation-Guided Development of Au-Catalyzed Cycloisomerizations Proceeding via 1,2-Si or 1,2-H Migrations: Regiodivergent Synthesis of Silylfurans".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 132.22(2010):7645-7655.
条目包含的文件
条目无相关文件。
个性服务
推荐该条目
保存到收藏夹
查看访问统计
导出为Endnote文件
谷歌学术
谷歌学术中相似的文章
[Dudnik, Alexander S.]的文章
[Xia, Yuanzhi]的文章
[Li, Yahong]的文章
百度学术
百度学术中相似的文章
[Dudnik, Alexander S.]的文章
[Xia, Yuanzhi]的文章
[Li, Yahong]的文章
必应学术
必应学术中相似的文章
[Dudnik, Alexander S.]的文章
[Xia, Yuanzhi]的文章
[Li, Yahong]的文章
相关权益政策
暂无数据
收藏/分享
所有评论 (0)
暂无评论
 

除非特别说明,本系统中所有内容都受版权保护,并保留所有权利。