Synthesis of α-Functionalized Trichloromethylcarbinols

Abstract

A new series of α-functionalized trichloromethylcarbinols have been synthesized from corresponding α-halomethyl ketones, esters, and amides in 48-78% overall yields. Reactivity of nitrates obtained in the first step was dependent on the electron-withdrawing nature of the functional groups, and increases with increasing electron deficiency. Synthetic applications of such trichloromethylcarbinols for the preparation of chloromethyl-α-diketones, trichloromethylated dihydrofurans, and enol acetates of α-functionalized acid chlorides have been demonstrated. The reaction of these compounds in the Jocic-Reeve reaction was also demonstrated.

Copper(I)‐Promoted Synthesis of Highly Substituted and Functionalized Tetrahydrothiophenes

“…The previous experience of our group in copper(I)‐catalysed radical cyclization reactions and an interest in exploring the radical cyclization reactions of less well‐studied systems such as β‐haloalkyl sulfides led us to devise a general method for the synthesis of highly functionalized β‐halogenated THTs through the Cu I ‐promoted 5‐ exo radical cyclization of easily accessible 1‐substituted 2,2,2‐trichloroethyl allyl thioethers.…”

Pd-catalyzed synthesis of 1-(hetero)aryl-2,2,2-trichloroethanols using chloral hydrate and (hetero)arylboroxines

“…One is an addition of the trichloromethyl anion to carbonyl compounds such as aldehydes or ketones (i). 7 This way has generally needed the use of toxic trichloromethyl anion sources such as chloroform and trichloroacetic acid. The other is an addition of moisture-sensitive organometallic reagents such as organomagnesium compounds to dehydrated chloral (ii).…”

A Straightforward Synthesis of Tribromomethyl Carbinols from Aldehydes and Bromoform with Potassium Hydroxide as the Catalyst

“…[9,10] The preparation of trihalomethyl carbinols mainly attributes to the nucleophilic addition of trichloromethide carbanions to aldehydes. Reported generation of trichloromethyl carbanions includes decarboxylation of sodium trichloroacetate in aprotic polar solvents [11,12] and alkalization of chloroform with a base [13][14][15][16][17][18][19][20] (Scheme 1 a). Tribromomethyl carbinols also was synthesized used BuLi / HMDS and KOH [21] with bromoform (Scheme 1).…”