标题：Theoretical Insight into the Au(I)-Catalyzed Intermolecular Condensation of Homopropargyl Alcohols with Terminal Alkynes: Reactant Stoichiometric Ratio-Controlled Chemodivergence
作者：Yang, Yiying; Li, Jinghua; Zhu, Rongxiu; Liu, Chengbu; Zhang, Dongju
作者机构：[Yang, Yiying; Zhu, Rongxiu; Liu, Chengbu; Zhang, Dongju] Shandong Univ, Inst Theoret Chem, Sch Chem & Chem Engn, Key Lab Colloid & Interface Chem,Min 更多
通讯作者：Zhu, Rongxiu;Zhu, RX;Zhang, DJ
通讯作者地址：[Zhu, RX; Zhang, DJ]Shandong Univ, Inst Theoret Chem, Sch Chem & Chem Engn, Key Lab Colloid & Interface Chem,Minist Educ, Jinan 250100, Shandong, Peop 更多
来源：JOURNAL OF ORGANIC CHEMISTRY
摘要：The mechanisms and chemoselectivities on the Au(I)-catalyzed intermolecular condensation between homopropargyl alcohols and terminal alkynes were investigated by performing DFT calculations. The reaction was indicated to involve three stages: transformation of the homopropargyl alcohol (R-1) via intramolecular cyclization to the cyclic vinyl ether (R-1'), formation of the C-2-arylalkynyl cyclic ether (P-1) via hydroalkynylation of R-1' with phenylacetylene (R-2), and conversion from P-1 to 2,3-dihydro-oxepine (P-2). The results revealed the origin of the reaction divergence and rationalized the experimental observations that a 1:3 reactant stoichiometric ratio affords P-1 as the major product, whereas the 1:1.1 ratio results in P-2 in high yield. The reactant stoichiometric ratio-controlled divergent reactivity is attributed to different catalytic activities of the gold catalyst toward different reaction stages. In the 1:3 situation, the excess R-2 induces the Au catalyst toward its dimerization and/or hydration, inhibiting the conversion of P-1 to P-2 and resulting in product P-1. Without excess R-2, the Au catalysis follows a general cascade reaction, leading to product P-2. Theoretical results described a general strategy controlling the reaction divergence by a different reactant stoichiometric ratio. This strategy may be enlightening for chemists who are exploring various synthesis methods with high chemo-, regio-, and enantioselectivities.