Fluorinated 2,6-Xylenesulfonyl Group: A Protective Group for Amines

Abstract

We have developed a fluorinated 2,6-xylenesulfonyl group (fluorinated xysyl, fXs) as a protective group for amines. The sulfonyl group could be attached to amines by reactions with the corresponding sulfonyl chloride, and survived various conditions, including acidic, basic, and even reductive conditions. The fXs group could be cleaved by treatment with a thiolate under mild conditions.

Entschützende Funktionalisierung: eine direkte Umwandlung von Nms‐Amiden in Carbonsäureamide

“…[11][12][13] Herkömmliche Benchmark-Sulfonamide wie Ns(nosyl)-Amide und Ts(tosyl)-Amide zwangen Chemiker jedoch in der Vergangenheit dazu, Kompromisse zwischen chemischer Stabilität und einer zuverlässigen und milden Entschützung einzugehen. Um dieses Problem anzugehen, haben unsere Gruppe und Yokoshimas Team kürzlich neu entwickelte Sulfonamid-Schutzgruppen eingeführt: Nms-Amide [14] und f Xs-Amide [15] (Schema 1B).…”

Nms‐Amides: An Amine Protecting Group with Unique Stability and Selectivity

“…Systematic in silico studies, which aided in assessing an array of potential arenesulfonyl groups, led to the identification of 2,4,6‐tris(trifluoromethyl)benzenesulfonyl chloride as a promising reagent for amine protection. Herein we report our results of the exploration of this reagent with regard to its installation, robustness and cleavage, and how it compares to current state‐of‐the‐art sulfonamide protecting groups in a variety of contexts [28] …”

“…Herein we report our results of the exploration of this reagent with regard to its installation, robustness and cleavage, and how it compares to current state‐of‐the‐art sulfonamide protecting groups in a variety of contexts. [28] …”

Deprotective Functionalization: A Direct Conversion of Nms‐Amides to Carboxamides Using Carboxylic Acids

“…[11][12][13] Conventional benchmark sulfonamides such as Ns(nosyl)-amides and Ts(tosyl)-amides, however, have historically forced chemists to compromise between chemical stability and a reliable and mild deprotection. To address this issue, our group and Yokoshima's team have recently introduced newly developed sulfonamide protecting groups: Nms-amides [14] and f Xs-amides [15] (Scheme 1B), respectively.…”