Matches in SemOpenAlex for { <https://semopenalex.org/work/W2739374300> ?p ?o ?g. }
- W2739374300 endingPage "2842" @default.
- W2739374300 startingPage "2832" @default.
- W2739374300 abstract "The mechanism of the Rh-catalyzed [5 + 1 + 2 + 1] cycloaddition of VCPs, terminal alkynes, and CO to yield hydroxydihydroindanones has been investigated by ωB97XD/SDD-6-31G* DFT calculations. The study has revealed the existence of two convergent cycloaddition pathways, [5 + 1 + 2 + 1] and [5 + 1 + 1 + 2], differing by only 2 kcal/mol. Both metal-catalyzed and off-metal electrocyclization/aromatization mechanisms for the final bicyclization reaction were investigated, with the traditional acid-catalyzed pathway dominating. The catalytic cycle is limited by the rate of alkyne insertion, which is consistent with mechanistic studies of the related [5 + 2] cycloaddition reaction. Monosubstituted alkyne insertion regioselectivity is kinetically controlled, with insertion via the unsubstituted alkyne terminus predominating. The alkyne insertion process does not appear to be sensitive to steric effects, with both the propyne and phenylacetylene model alkynes showing similar selectivities (TS energy differences of ca. 5 kcal/mol in both cases for the two regioisomeric transition states). C–C bond activation of disubstituted vinylcyclopropanes was investigated, suggesting that activation of the least substituted C–C bond is preferred unless an electron-withdrawing group is present on the VCP, in which case the most substituted bond will be cleaved." @default.
- W2739374300 created "2017-07-31" @default.
- W2739374300 creator A5059482268 @default.
- W2739374300 creator A5085137159 @default.
- W2739374300 date "2017-07-21" @default.
- W2739374300 modified "2023-10-02" @default.
- W2739374300 title "[5 + 1 + 2 + 1] vs [5 + 1 + 1 + 2] Rhodium-Catalyzed Cycloaddition Reactions of Vinylcyclopropanes with Terminal Alkynes and Carbon Monoxide: Density Functional Theory Investigations of Convergent Mechanistic Pathways and Reaction Regioselectivity" @default.
- W2739374300 cites W1963565960 @default.
- W2739374300 cites W1967606898 @default.
- W2739374300 cites W1971692273 @default.
- W2739374300 cites W1971829436 @default.
- W2739374300 cites W1973053405 @default.
- W2739374300 cites W1973096409 @default.
- W2739374300 cites W1975869640 @default.
- W2739374300 cites W1976407428 @default.
- W2739374300 cites W1980252409 @default.
- W2739374300 cites W1982356449 @default.
- W2739374300 cites W1983837010 @default.
- W2739374300 cites W1994140434 @default.
- W2739374300 cites W2001585347 @default.
- W2739374300 cites W2007608151 @default.
- W2739374300 cites W2008130777 @default.
- W2739374300 cites W2011215428 @default.
- W2739374300 cites W2011295666 @default.
- W2739374300 cites W2015723183 @default.
- W2739374300 cites W2021918596 @default.
- W2739374300 cites W2022975013 @default.
- W2739374300 cites W2023271753 @default.
- W2739374300 cites W2027823748 @default.
- W2739374300 cites W2029266122 @default.
- W2739374300 cites W2030925977 @default.
- W2739374300 cites W2036640855 @default.
- W2739374300 cites W2041870822 @default.
- W2739374300 cites W2044128456 @default.
- W2739374300 cites W2044875465 @default.
- W2739374300 cites W2045830377 @default.
- W2739374300 cites W2047531388 @default.
- W2739374300 cites W2048121052 @default.
- W2739374300 cites W2050791488 @default.
- W2739374300 cites W2053346023 @default.
- W2739374300 cites W2054155646 @default.
- W2739374300 cites W2054246966 @default.
- W2739374300 cites W2055638152 @default.
- W2739374300 cites W2056073623 @default.
- W2739374300 cites W2063430105 @default.
- W2739374300 cites W2063449880 @default.
- W2739374300 cites W2065675348 @default.
- W2739374300 cites W2073670208 @default.
- W2739374300 cites W2075384695 @default.
- W2739374300 cites W2077575394 @default.
- W2739374300 cites W2081724295 @default.
- W2739374300 cites W2091567820 @default.
- W2739374300 cites W2100272408 @default.
- W2739374300 cites W2104742517 @default.
- W2739374300 cites W2111498252 @default.
- W2739374300 cites W2112798528 @default.
- W2739374300 cites W2112850441 @default.
- W2739374300 cites W2124824532 @default.
- W2739374300 cites W2126636908 @default.
- W2739374300 cites W2127336290 @default.
- W2739374300 cites W2135684593 @default.
- W2739374300 cites W2143981217 @default.
- W2739374300 cites W2149731084 @default.
- W2739374300 cites W2155358697 @default.
- W2739374300 cites W2158397444 @default.
- W2739374300 cites W2160999136 @default.
- W2739374300 cites W2163313338 @default.
- W2739374300 cites W2167248026 @default.
- W2739374300 cites W2172295873 @default.
- W2739374300 cites W2173728066 @default.
- W2739374300 cites W2270107860 @default.
- W2739374300 cites W2322162786 @default.
- W2739374300 cites W2322929798 @default.
- W2739374300 cites W2324856471 @default.
- W2739374300 cites W2325096660 @default.
- W2739374300 cites W2326196070 @default.
- W2739374300 cites W2334262731 @default.
- W2739374300 cites W2334267937 @default.
- W2739374300 cites W2334379385 @default.
- W2739374300 cites W2338230418 @default.
- W2739374300 cites W2339100111 @default.
- W2739374300 cites W2394849480 @default.
- W2739374300 cites W2394986350 @default.
- W2739374300 cites W2472789359 @default.
- W2739374300 cites W2490635023 @default.
- W2739374300 cites W2515388800 @default.
- W2739374300 cites W2949628318 @default.
- W2739374300 cites W2949628629 @default.
- W2739374300 cites W2949838858 @default.
- W2739374300 cites W2950058448 @default.
- W2739374300 cites W2950217643 @default.
- W2739374300 cites W2950724854 @default.
- W2739374300 cites W2950725863 @default.
- W2739374300 cites W2950942420 @default.
- W2739374300 cites W2951530118 @default.
- W2739374300 cites W2951795836 @default.
- W2739374300 cites W2951899654 @default.
- W2739374300 cites W2952280130 @default.