Unexpected dual orbital effects in radical addition reactions involving acyl, silyl and related radicals.
نویسندگان
چکیده
Molecular orbital calculations reveal that acyl and silyl radicals add to numerous types of pi-systems through simultaneous SOMO-LUMO and LUMO-HOMO interactions of the radical with the radicalophile respectively.
منابع مشابه
Radicals masquerading as electrophiles: a computational study of the intramolecular addition reactions of acyl radicals to imines.
Ab initio calculations using 6-311G**, cc-pVDZ, and aug-cc-pVDZ, with (MP2, QCISD, CCSD(T)) and without (UHF) electron correlation, and density functional methods (BHandHLYP and B3LYP) predict that cyclization of the 5-aza-5-hexenoyl and (E)-6-aza-5-hexenoyl radicals proceed to afford the 5-exo products. At the CCSD(T)/cc-pVDZ//BHandHLYP/cc-pVDZ level of theory, energy barriers (deltaE(double d...
متن کاملGeneration of radical species by one electron oxidation with metallic compounds for the construction of carbon skeletons
By oxidation of P-keto acids, cyclopropanols, and acyl chromate complexes with tris(2-pyridinecarboxylato)manganese(III) (Mn(pic)g), a-keto, p-keto, and alkyl radicals are generated respectively, which react with olefinic compounds to afford intermolecular addition products in good yield. The cation radicals can be generated from a-stannylalkyl sulfides, (1 -stannylalkyl)amino compounds, and a-...
متن کاملPhosphinoyl Radicals: Structure and Reactivity. A Laser Flash Photolysis and Time-Resolved ESR Investigation
The photochemistry of a series of bis(acyl)phosphine oxides and the rate constants of the reactions of their phosphorus radicals with n-butylacrylate, thiophenol, bromotrichloromethane, oxygen, and methyl viologen have been investigated by laser flash photolysis. The results were compared to a mono(acyl)phosphine oxide ((2,4,6-trimethylbenzoyl)diphenylphosphine oxide). The variation in reactivi...
متن کاملFree radical macrophotoinitiators: an overview on recent advances
This paper provides an overview of the recent advances on polymeric photoinitiators for UV curing. During the last decade, significant developments have been achieved in the synthesis of macrophotoinitiators, due to the advantages derived of their macromolecular nature, in comparison with their corresponding low molecular weight analogues. In particular, a variety of macromolecules containing t...
متن کاملFirst determination of the rate constant for ring-closure of an azahexenoyl radical: 6-aza-7-ethyl-5-hexenoylw
It is now well established that radical carbonylation chemistry is useful for the construction of heterocycles. For example, one of us has shown that, unlike alkyl radicals, acyl radicals formed by the reaction of alkyl radicals with carbon monoxide are N-philic and react to form a variety of lactams (Scheme 1). These observations have been rationalised as being the result of multiorbital inter...
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 10 شماره
صفحات -
تاریخ انتشار 2006