2362-61-0Relevant articles and documents
trans-2-Phenylcyclohexanol. A Powerful and Readily Available Chiral Auxiliary
Whitesell, James K.,Chen, Hwang-Hsing,Lawrence, Robert M.
, p. 4663 - 4664 (1985)
The title alcohol has been shown to be a powerful and readily available chiral auxiliary for use in ene reactions of the derived glyoxylate ester.
BiCl3-Facilitated removal of methoxymethyl-ether/ester derivatives and DFT study of -O-C-O- bond cleavage
Pacherille, Angela,Tuga, Beza,Hallooman, Dhanashree,Dos Reis, Isaac,Vermette, Mélodie,Issack, Bilkiss B.,Rhyman, Lydia,Ramasami, Ponnadurai,Sunasee, Rajesh
supporting information, p. 7109 - 7116 (2021/05/03)
A simple method for the cleavage of methoxymethyl (MOM)-ether and ester derivatives using bismuth trichloride (BiCl3) is described. The alkyl, alkenyl, alkynyl, benzyl and anthracene MOM ether derivatives, as well as MOM esters of both aliphatic and aromatic carboxylic acids, were deprotected in good yields. To better understand the molecular roles of BiCl3and water for MOM cleavage, two possible binding pathways were investigated using the density functional theory (DFT) method. The theoretical results indicate the differential initial binding site preferences of phenolic and alcoholic MOM substrates to the Bi atom and suggest that water plays a key role in facilitating the cleavage of the MOM group.
Chemoselective Oxidation of Equatorial Alcohols with N-Ligated λ3-Iodanes
Mikhael, Myriam,Adler, Sophia A.,Wengryniuk, Sarah E.
, p. 5889 - 5893 (2019/08/26)
The site-selective and chemoselective functionalization of alcohols in complex polyols remains a formidable synthetic challenge. Whereas significant advancements have been made in selective derivatization at the oxygen center, chemoselective oxidation to the corresponding carbonyls is less developed. In cyclic systems, whereas the selective oxidation of axial alcohols is well known, a complementary equatorial selective process has not yet been reported. Herein we report the utility of nitrogen-ligated (bis)cationic λ3-iodanes (N-HVIs) for alcohol oxidation and their unprecedented levels of selectivity for the oxidation of equatorial over axial alcohols. The conditions are mild, and the simple pyridine-ligated reagent (Py-HVI) is readily synthesized from commercial PhI(OAc)2 and can be either isolated or generated in situ. Conformational selectivity is demonstrated in both flexible 1,2-substituted cyclohexanols and rigid polyol scaffolds, providing chemists with a novel tool for chemoselective oxidation.
(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.
