Nickel(0)/NaHMDS adduct-mediated intramolecular alkylation of unactivated arenes via a homolytic aromatic substitution mechanism.
نویسندگان
چکیده
A variety of polycycles can be synthesized via an intramolecular alkylation cyclization promoted by Ni(PPh(3))(4) and NaHMDS. Mechanistic investigations support the catalytic nature of Ni(0) in the course of TEMPO scavenging experiments and its association with the substrate and NaHMDS to form an adduct by DOSY NMR.
منابع مشابه
Metal-free oxidative decarbonylative coupling of aromatic aldehydes with arenes: direct access to biaryls.
A metal-free oxidative decarbonylative coupling of aromatic aldehydes with electron-rich or electron-deficient arenes to produce biaryl compounds was developed. This novel coupling was proposed to proceed via a non-chain radical homolytic aromatic substitution (HAS) type mechanism, based on the substrate scope, ortho-regioselectivity, radical trapping experiments and DFT calculation studies. Wi...
متن کاملThe study of metal-free and palladium-catalysed synthesis of benzochromenes via direct C–H arylation using unactivated aryl benzyl ethers derived from essential oils as raw materials†
The synthesis of 6H-benzo[c]chromenes from unactivated 2-bromo aryl benzyl ethers was studied through two approaches: (i) the transition-metal-free intramolecular dehydrohalide coupling via intramolecular homolytic aromatic substitution; and (ii) the intramolecular cyclization via direct C–H arylation catalysed by PdCl2(MeCN)2. Having developed the most efficient method, a 17-membered chromene ...
متن کاملThrough-Space Activation Can Override Substituent Effects in Electrophilic Aromatic Substitution.
Electrophilic aromatic substitution (EAS) represents one of the most important classes of reactions in all of chemistry. One of the "iron laws" of EAS is that an electron-rich aromatic ring will react more rapidly than an electron-poor ring with suitable electrophiles. In this report, we present unique examples of electron-deficient arenes instead undergoing preferential substitution in intramo...
متن کاملAmine α-heteroarylation via photoredox catalysis: a homolytic aromatic substitution pathway.
The direct α-heteroarylation of tertiary amines has been accomplished via photoredox catalysis to generate valuable benzylic amine pharmacophores. A variety of five-and six-membered chloroheteroarenes are shown to function as viable coupling partners for the α-arylation of a diverse range of cyclic and acyclic amines. Evidence is provided for a homolytic aromatic substitution mechanism, in whic...
متن کاملDirect intramolecular arylation of unactivated arenes: application to the synthesis of aporphine alkaloids.
The direct intramolecular C-H arylation of unactivated arenes is a viable strategy for the synthesis of aporphine alkaloids. These reactions occur with 3 to 5 mol% catalyst and generate the aporphine skeleton in up to 99% yield.
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 48 66 شماره
صفحات -
تاریخ انتشار 2012