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• W2099205910 endingPage "5415" @default.
• W2099205910 startingPage "5401" @default.
• W2099205910 abstract "A comprehensive mechanistic study of the InCl3-, AuCl-, and PtCl2-catalyzed cycloisomerization of the 2-(haloethynyl)biphenyl derivatives of Fürstner et al. was carried out by DFT/M06 calculations to uncover the catalyst-dependent selectivity of the reactions. The results revealed that the 6-endo-dig cyclization is the most favorable pathway in both InCl3- and AuCl-catalyzed reactions. When AuCl is used, the 9-bromophenanthrene product could be formed by consecutive 1,2-H/1,2-Br migrations from the Wheland-type intermediate of the 6-endo-dig cyclization. However, in the InCl3-catalyzed reactions, the chloride-assisted intermolecular H-migrations between two Wheland-type intermediates are more favorable. These Cl-assisted H-migrations would eventually lead to 10-bromophenanthrene through proto-demetalation of the aryl indium intermediate with HCl. The cause of the poor selectivity of the PtCl2 catalyst in the experiments by the Fürstner group was predicted. It was found that both the PtCl2-catalyzed alkyne–vinylidene rearrangement and the 5-exo-dig cyclization pathways have very close activation energies. Further calculations found the former pathway would lead eventually to both 9- and 10-bromophenanthrene products, as a result of the Cl-assisted H-migrations after the cyclization of the Pt–vinylidene intermediate. Alternatively, the intermediate from the 5-exo-dig cyclization would be transformed into a relatively stable Pt–carbene intermediate irreversibly, which could give rise to the 9-alkylidene fluorene product through a 1,2-H shift with a 28.1 kcal mol−1 activation barrier. These findings shed new light on the complex product mixtures of the PtCl2-catalyzed reaction." @default.
• W2099205910 created "2016-06-24" @default.
• W2099205910 creator A5029978416 @default.
• W2099205910 creator A5031724407 @default.
• W2099205910 creator A5039771089 @default.
• W2099205910 creator A5044249581 @default.
• W2099205910 creator A5051427074 @default.
• W2099205910 date "2012-03-20" @default.
• W2099205910 modified "2023-10-13" @default.
• W2099205910 title "Mechanism of the Transition-Metal-Catalyzed Hydroarylation of Bromo-Alkynes Revisited: Hydrogen versus Bromine Migration" @default.
• W2099205910 cites W1963688013 @default.
• W2099205910 cites W1964255980 @default.
• W2099205910 cites W1965396770 @default.
• W2099205910 cites W1965414986 @default.
• W2099205910 cites W1966182479 @default.
• W2099205910 cites W1967429049 @default.
• W2099205910 cites W1969506788 @default.
• W2099205910 cites W1974323347 @default.
• W2099205910 cites W1974891172 @default.
• W2099205910 cites W1975869640 @default.
• W2099205910 cites W1976523895 @default.
• W2099205910 cites W1976603595 @default.
• W2099205910 cites W1977048585 @default.
• W2099205910 cites W1978502773 @default.
• W2099205910 cites W1979155729 @default.
• W2099205910 cites W1979737296 @default.
• W2099205910 cites W1980892807 @default.
• W2099205910 cites W1981344834 @default.
• W2099205910 cites W1982524148 @default.
• W2099205910 cites W1982910562 @default.
• W2099205910 cites W1983048151 @default.
• W2099205910 cites W1984471932 @default.
• W2099205910 cites W1985046288 @default.
• W2099205910 cites W1986397872 @default.
• W2099205910 cites W1986793444 @default.
• W2099205910 cites W1989096505 @default.
• W2099205910 cites W1989105465 @default.
• W2099205910 cites W1989503809 @default.
• W2099205910 cites W1991058593 @default.
• W2099205910 cites W1993264007 @default.
• W2099205910 cites W1996869414 @default.
• W2099205910 cites W1998085037 @default.
• W2099205910 cites W1998375603 @default.
• W2099205910 cites W1998960008 @default.
• W2099205910 cites W2006464200 @default.
• W2099205910 cites W2007332006 @default.
• W2099205910 cites W2008164789 @default.
• W2099205910 cites W2009079573 @default.
• W2099205910 cites W2009704081 @default.
• W2099205910 cites W2010741465 @default.
• W2099205910 cites W2011119306 @default.
• W2099205910 cites W2011180004 @default.
• W2099205910 cites W2014293111 @default.
• W2099205910 cites W2014588626 @default.
• W2099205910 cites W2014767176 @default.
• W2099205910 cites W2018422533 @default.
• W2099205910 cites W2019011827 @default.
• W2099205910 cites W2019263180 @default.
• W2099205910 cites W2020339731 @default.
• W2099205910 cites W2021130826 @default.
• W2099205910 cites W2022890554 @default.
• W2099205910 cites W2023714554 @default.
• W2099205910 cites W2024611042 @default.
• W2099205910 cites W2024916206 @default.
• W2099205910 cites W2025002140 @default.
• W2099205910 cites W2026587615 @default.
• W2099205910 cites W2026786332 @default.
• W2099205910 cites W2027252952 @default.
• W2099205910 cites W2028632252 @default.
• W2099205910 cites W2030646984 @default.
• W2099205910 cites W2031644569 @default.
• W2099205910 cites W2031885077 @default.
• W2099205910 cites W2032284574 @default.
• W2099205910 cites W2034666141 @default.
• W2099205910 cites W2036424911 @default.
• W2099205910 cites W2037964091 @default.
• W2099205910 cites W2040122123 @default.
• W2099205910 cites W2042915585 @default.
• W2099205910 cites W2044490585 @default.
• W2099205910 cites W2044673682 @default.
• W2099205910 cites W2045403760 @default.
• W2099205910 cites W2046412723 @default.
• W2099205910 cites W2046838573 @default.
• W2099205910 cites W2048683089 @default.
• W2099205910 cites W2049249446 @default.
• W2099205910 cites W2049272799 @default.
• W2099205910 cites W2051681766 @default.
• W2099205910 cites W2054246966 @default.
• W2099205910 cites W2057005783 @default.
• W2099205910 cites W2057747671 @default.
• W2099205910 cites W2058936090 @default.
• W2099205910 cites W2058965706 @default.
• W2099205910 cites W2059093614 @default.
• W2099205910 cites W2060850694 @default.
• W2099205910 cites W2066461259 @default.
• W2099205910 cites W2068617439 @default.
• W2099205910 cites W2070048051 @default.
• W2099205910 cites W2071202150 @default.

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