Journal
ASIAN JOURNAL OF ORGANIC CHEMISTRY
Volume 6, Issue 12, Pages 1885-1892Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ajoc.201700469
Keywords
alkynes; annulation; density functional calculations; reaction mechanisms; rhodium
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Funding
- Natural Science Foundation of Shandong Province [ZR2016BM09, ZR2014BL013, ZR2015BL013]
- National Training Program of Innovation and Entrepreneurship for Undergraduates [201610454011, 201610454019]
- Talent Team Culturing Plan for Leading Disciplines of University in Shandong
- Youth Fund of Jining University [2016QNKJ03]
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A mechanistic study of the Cp*Rh-III-catalyzed (Cp*=(5)-pentamethylcyclopentadienyl) intramolecular redox-neutral annulation of tethered alkynes was carried out by density functional calculations using the M06 method. Our results show that the reductive elimination step of the catalytic cycle is rate determining, and the overall energy barrier of the entire process is 31.4kcalmol(-1) (L-IIL-TS8-9). This is in agreement with experimental results that reported the C-H bond cleavage not to be the rate-determining step. According to our calculations, the feasible mechanism for the (RhRhRhIII)-Rh-III-Rh-V process involves an acylamino migration and subsequent reductive elimination process, which is different from the pathway previously proposed by Li's group. The present calculations elucidate the experimental observations on the molecular level.
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