99306-80-6Relevant academic research and scientific papers
Transition-Metal-Free Allylic Borylation of 1,3-Dienes
Maza, Ricardo J.,Davenport, Elliot,Miralles, Núria,Carbó, Jorge J.,Fernández, Elena
supporting information, p. 2251 - 2255 (2019/04/10)
This work explains the reactivity of diboron reagents with 1,3-dienes in a transition-metal-free context. The sole addition of Na2CO3 (30 mol %) to bis(pinacolato)diboron in MeOH allows the 1,4-hydroboration of cyclic and noncyclic 1,3-dienes. The electronic influence on the substrate guarantees the conjugated 1,4-hydroboration versus 1,2-diboration. DFT calculations show that the distribution of charge in the allylic anion intermediate governs the selectivity toward 1,4-hydroboration, while the favored trans configuration in diene reagents determines the preference for the E allyl boronate products.
An efficient procedure for the 1,3-transposition of allylic alcohols based on lithium naphthalenide induced reductive elimination of epoxy mesylates
Wu, Yen-Ku,Liu, Hsing-Jang,Zhu, Jia-Liang
, p. 621 - 623 (2008/12/22)
An efficient protocol for the 1,3-transposition of allylic alcohols has been developed. The method is based on the pretransformation of allylic alcohols into the corresponding epoxy mesylates, followed by the reductive elimination of the resulting epoxy mesylates by using lithium naphthalenide (LN) as a reducing agent. Georg Thieme Verlag Stuttgart.
Stereoselective preparation of 2-silylated 1,3-diols and the regioselectivity of their peterson olefination
Faessler, Juerg,Linden, Anthony,Bienz, Stefan
, p. 1717 - 1730 (2007/10/03)
The reduction of the carbonyl group of α-silylated aldols with complex hydrides was shown to proceed with high stereoselectivity. The center of chirality in the α-position to the ketone, at the C-atom where the silicon group is attached, usually dominated the stereochemical control of the reaction. The presence of the β-hydroxy functionality, however, also seems to be necessary for a high degree of selectivity. Peterson olefination of 2- silylated 1,3-diols afforded stereoselectively (E)-configured allylic alcohols as the major products. With KH as the base, the reaction proceeds predominantly in a syn-fashion, preferring to eliminate a syn- rather than an anti-configured β-hydroxysilane unit. Under 'silico-nucleophilic' conditions (OH- or F-), an anti-configured β-hydroxysilane moiety can also be eliminated in an anti-fashion. This reaction is strongly preferred over the corresponding syn-elimination, but is still less prominent than a competitive syn-elimination of a syn-configured β-hydroxysilane unit.
Stereochemistry of the Epoxidations of Acyclic Allylic Amides. Applications toward the Synthesis of 2,3,6-Trideoxy-3-aminohexoses
Roush, William R.,Straub, Julie A.,Brown, Richard J.
, p. 5127 - 5136 (2007/10/02)
The stereochemistry of the epoxidation of several acyclic allylic amides is described.Diastereoselectivity in the (Z)-allylic amide series (compound 1) proved to be dependent both on the amide functionality and epoxidation reagent.The threo epoxide 3 was
FACILE SYNTHESIS OF (E)-ALLYLIC ALCOHOLS BY ACID-CATALYZED MODIFICATION OF THE MISLOW-EVANS REARRANGEMENT OF ALLYLIC SULFOXIDES
Masaki, Yukio,Sakuma, Kazuhiko,Kaji, Kenji
, p. 2531 - 2534 (2007/10/02)
The Mislow-Evans rearrangement of α,β- and α,γ-disubstituted allylic sulfoxides (2) to (E)-allylic alcohols (4) was found to occur under acidic conditions.By combination of this method with a catalytic oxidation of allylic sulfides (1), a novel one-pot tr
