2362-73-4Relevant articles and documents
(Poly)cationic λ3-Iodane-Mediated Oxidative Ring Expansion of Secondary Alcohols
Walters, Jennifer C.,Tierno, Anthony F.,Dubin, Aimee H.,Wengryniuk, Sarah E.
supporting information, p. 1460 - 1464 (2018/04/06)
Herein, a simplified approach to the synthesis of medium-ring ethers through the electrophilic activation of secondary alcohols with (poly)cationic λ3-iodanes (N-HVIs) is reported. Excellent levels of selectivity are achieved for C–O bond migration over established α-elimination pathways, enabled by the unique reactivity of a novel 2-OMe-pyridine-ligated N-HVI. The resulting hexafluoroisopropanol (HFIP) acetals are readily derivatized with a range of nucleophiles, providing a versatile functional handle for subsequent manipulations. The utility of this methodology for late-stage natural product derivatization was also demonstrated, providing a new tool for diversity-oriented synthesis and complexity-to-diversity (CTD) efforts. Preliminary mechanistic investigations reveal a strong effect of alcohol conformation on the reactive pathway, thus providing a predictive power in the application of this approach to complex molecule synthesis.
Kinetic resolution of secondary alcohols catalyzed by chiral phosphoric acids
Harada, Shingo,Kuwano, Satoru,Yamaoka, Yousuke,Yamada, Ken-Ichi,Takasu, Kiyosei
, p. 10227 - 10230 (2013/10/21)
Acid instead of base: Kinetic resolution of secondary alcohols is realized using chiral Bronsted acid catalyzed acylation instead of the conventional basic conditions. A broad range of functional groups are tolerated, such as aldehydes, carboxylic acids, and enoates. The selectivity factor (s) reaches up to 215 at ambient temperature. Copyright
Diastereoselective reduction of alkenylboronic esters as a new method for controlling the stereochemistry of up to three adjacent centers in cyclic and acyclic molecules
Hupe, Eike,Marek, Ilan,Knochel, Paul
, p. 2861 - 2863 (2007/10/03)
(figure presented) cis-Boronates are readily available via a diastereoselective Pd-catalyzed reduction of tetrasubstituted alkenylboronic esters using H2. Applying the reaction conditions presented to unsaturated open-chain boronic esters allows the stereochemistry of up to three adjacent centers to be controlled.