Enantioselective synthesis of gamma-hydroxyenones by chiral base-catalyzed Kornblum DeLaMare rearrangement.
نویسندگان
چکیده
A cinchona-alkaloid catalyzed asymmetric Kornblum DeLaMare rearrangement has been developed. Thus, enantioenriched 4-hydroxyenones are prepared from dienes by a two-step sequence involving photochemical dioxygenation and chiral base-catalyzed desymmetrization of the resulting endoperoxides.
منابع مشابه
Studies on the Mechanism of Base-Catalyzed Decomposition of Bicyclic Endoperoxides
Kornblum and Delamare showed the first decomposition of dialkyl peroxides by base-catalyzed rearrangement. They reported that 1-[1-(tert -butylperoxy)ethyl] benzene 1 gives acetophenone and tert-butanol by treatment with bases such as KOH, NaOEt, and piperidine. Milas and Surgenor reported previously the stability of 2-(tert -butylperoxy)-2-methylpropane against strong bases. Kornblum and Delam...
متن کاملEnantioselective rhodium-catalyzed addition of potassium alkenyltrifluoroborates to cyclic imines.
Chiral α-branched allylic amines are important building blocks for organic synthesis, and several catalytic asymmetric methods have been developed for their synthesis. For example, enantioselective metal-catalyzed amination of allylic electrophiles 1 , 2 , 3 ] and rearrangement of allylic imidates have proven to be highly effective. An alternative approach to chiral allylic amines that can be a...
متن کاملChiral (acyclic diaminocarbene)gold(I)-catalyzed dynamic kinetic asymmetric transformation of propargyl esters.
A highly enantioselective transformation catalyzed by chiral (acyclic diaminocarbene)gold(I) complexes is reported. The enantioselective synthesis of 2-substituted chromenyl pivalates from racemic phenol-substituted propargyl pivalates was developed. Rearrangement of the substrates in the presence of cationic gold gave allene intermediates, whose cyclization resulted in formation of enantioenri...
متن کاملEnantioselective Synthesis of Modafinil Drug using Chiral Complex of Titanium and Diethyltartarate
Modafinil (Diphenyl methyl Sulfinyl acetamid) is used clinically in the treatment of narcolepsy and sleeping disorders. The synthesis of R-modafinil, have started with the reaction of benzhydrol and thioglycolic acid in trifluoroacetic acid to afford benzhydryl sulfanyl acetic acid. The reaction of acid with thionyl chloride in benzene followed by treatment with ammonium hydroxide gave acetamid...
متن کاملEnantioselective Black rearrangement catalyzed by chiral bicyclic imidazole.
A newly developed chiral imidazole nucleophilic catalyst, , was readily prepared and successfully applied to the enantioselective Black rearrangement with up to 88% ee for a wide range of substrates possessing different substituted groups. A plausible mechanism for the high enantioselectivity was proposed.
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:
- Journal of the American Chemical Society
دوره 128 39 شماره
صفحات -
تاریخ انتشار 2006