Practical access to axially chiral sulfonamides and biaryl amino phenols via organocatalytic atroposelective N-alkylation

Abstract

The importance of axial chirality in enantioselective synthesis has been widely recognized for decades. The practical access to certain structures such as biaryl amino phenols known as NOBINs in enantiopure form, however, still remains a challenge. In drug delivery, the incorporation of axially chiral molecules in systematic screening has also received a great deal of interest in recent years, which calls for innovation and practical synthesis of structurally different axially chiral entities. Herein we present an operationally simple catalytic N -alkylation of sulfonamides using commercially available chiral amine catalysts to deliver two important classes of axially chiral compounds: structurally diverse NOBIN analogs as well as axially chiral N -aryl sulfonamides in excellent enantiopurity. Structurally related chiral sulfonamide has shown great potential in drug molecules but enantioselective synthesis of them has never been accomplished before. The practical catalytic procedures of our methods also bode well for their wide application in enantioselective synthesis.

Stimuli Responsive Materials Supported by Orthogonal Hydrogen and Halogen Bonding or I···Alkene Interaction

“…). This survey reveals that only four molecules adopt the same structural motif, namely HOQKAC [35], HOTZOH [36], PEQVOZ [37] and USAJIK [38]. In these X-ray structures, the I•••C interactions appear much weaker than in I-azo-NH-MMA, since the I•••CH 2 =C distances are in the range of 3.526-3.692 Å (Figure S1, Supplementary Materials).…”

Multi Stimuli Responsive Materials Supported by Orthogonal Hydrogen and Halogen Bonding or I···Alkene Interaction

“…). This survey reveals that only four molecules adopt the same structural motif, namely HOQKAC, [35] HOTZOH, [36] PEQVOZ [37] and USAJIK. [38] In these X-ray structures, the I•••C interactions appear much weaker than in I-azo-NH-MMA, since the I•••CH2=C distances are in the range of 3.526-3.692 Å (Figure S1).…”

“…X-ray structure of I-azo-NH-MMA developing undulating parallel chains due to C•••I halogen bonds This intriguing contact convinced us to make a Cambridge Structural Database (CSD version 5.42 updates, Sep 2021) analysis on the interaction between an iodine and a double bond (I•••CH2=C). This survey reveals that only four molecules adopt the same structural motif, namely HOQKAC,[35] HOTZOH,[36] PEQVOZ[37] and USAJIK [38]. In these X-ray structures, the I•••C interactions appear much weaker than in I-azo-NH-MMA, since the…”

[3,3] Sigmatropic Shifts and Applications of Hydroxylamine Derivatives

“…得到消旋的 NOBIN 型化合物之后, 对消旋产物进 行了动力学拆分. 在综合考虑手性相转移催化剂介导的 O-H 键烷基化 [43] , 金鸡纳生物碱衍生的手性胺催化的 图式 13 通过芳基季铵盐合成 NOBIN 型化合物 Scheme 13 Synthesis of NOBIN-type products from arylammonium salts N-烷基化 [44] 与 N-杂环卡宾(NHC)催化的 O-H 基团酰化 等方法后 [45][46][47] , 选择了在 DQ [3,3',5,5'-tetra(tert-butyl)- [1,10- 通过 N,O-二烯基羟胺的 [3,3] σ 迁移反应可以使用 简单的底物, 以温和的条件制备多种脱氧核苷类似物, 在生物化学与药物化学领域具有较大的应用价值 [51] . [53] , 通过 N-O 键断裂的 [3,3] [60] .…”