Unprecedented directed lateral lithiations of tertiary carbons on NHC platforms.
نویسندگان
چکیده
Unexpected and unprecedented directed remote lateral lithiation at one CH(CH3)2 of the 3-(2,6-di-isopropylphenyl) wingtip took place upon the reaction of functionalised N-heterocyclic carbene-type molecules with excess of LiCH2SiMe3, leading to dilithiated dianionic 4-amido-N-heterocyclic carbenes. DFT calculations show that the nature of the isolated species are under thermodynamic control.
منابع مشابه
Sc3N@Ih-C80 as a novel Lewis acid to trap abnormal N-heterocyclic carbenes: the unprecedented formation of a singly bonded [6,6,6]-adduct
The reaction between an N-heterocyclic carbene (NHC), namely 1,3-bis(diisopropylphenyl)-imidazol-2ylene (1), and Sc3N@Ih-C80 successfully affords a Lewis acid–base pair (2a). Single crystal X-ray crystallographic results unambiguously reveal the unexpected structure of 2a where the abnormal carbene center of the NHC is connected to a triple-hexagon-junction (THJ) carbon atom of Sc3N@IhC80 via a...
متن کاملDouble activation of an N-alkylimidazole.
Despite the extensive coordination chemistry of imidazoles, metal-mediated imidazole activation is very rare. It has been shown that deprotonation of the central C-H group of coordinated N-alkylimidazoles can serve, after reaction of the resulting imidazolyl intermediate with an electrophile, as a new synthetic route to N-heterocyclic carbene (NHC) complexes. NHC ligands, which attract much ong...
متن کاملCarbene-catalysed reductive coupling of nitrobenzyl bromides and activated ketones or imines via single-electron-transfer process
Benzyl bromides and related molecules are among the most common substrates in organic synthesis. They are typically used as electrophiles in nucleophilic substitution reactions. These molecules can also be activated via single-electron-transfer (SET) process for radical reactions. Representative recent progress includes α-carbon benzylation of ketones and aldehydes via photoredox catalysis. Her...
متن کاملNew geodynamical model for the regional Tertiary extension during the Zagros orogeny: A transtensional arc?
The Zagros orogeny in Iran is associated with two successive geodynamic events during the Tertiary period, a Paleogene NE-directed regional crustal extension followed by a Miocene NW-directed regional crustal extension and a magmatic flare-up. The current study was undertaken to reanalyze previous structural work developed on the extensional Chapedony metamorphic core complex in Central Iran ex...
متن کاملNi-catalysed, domino synthesis of tertiary alcohols from secondary alcohols.
The use of in situ generated (NHC)-Ni catalytic species (NHC = N-heterocyclic carbene) allows for the synthesis, in short reaction times, of a variety of tertiary alcohols from secondary alcohols through a domino oxidation-addition protocol.
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Chemical communications
دوره 51 15 شماره
صفحات -
تاریخ انتشار 2015