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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
Source PublicationJOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume132Issue:22Pages:7645-7655
SubtypeArticle
AbstractA 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 HeadingsScience & Technology ; Physical Sciences
WOS KeywordHOMOGENEOUS GOLD CATALYSIS ; HIGHLY SUBSTITUTED FURANS ; EFFICIENT SYNTHESIS ; POLYSUBSTITUTED FURANS ; TETRASUBSTITUTED FURANS ; 2,5-DISUBSTITUTED FURANS ; CASCADE REACTIONS ; ALLENYL SULFIDES ; PI-ACIDS ; HETEROCYCLES
Indexed BySCI ; IC ; CCR
Language英语
WOS Research AreaChemistry
WOS SubjectChemistry, Multidisciplinary
WOS IDWOS:000278837100023
Citation statistics
Document Type期刊论文
Identifierhttp://ir.isl.ac.cn/handle/363002/5954
Collection青海盐湖研究所知识仓储
Affiliation1.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
Recommended Citation
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.
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