A Post‐Modification Strategy for the Synthesis of Uniform, Hydrophilic/Hydrophobic Patterned α‐Hydroxy Acid Oligomers

Abstract

Hydrophilic/hydrophobic patterning is a well-established design strategy to guide secondary structure formation of both natural as well as non-natural oligomers and polymers. This contribution explores the feasibility of a new approach for the synthesis of uniform, sequence-defined, hydrophilic/ hydrophobic patterned oligo(α-hydroxy acid)s. The proposed strategy is based on post-modification of a reactive oligoester scaffold composed of an alternating sequence of hydrophobic [(2S)-2-hydroxy-4-methylpentanoic acid] and masked hydrophilic [(2S)-2-hydroxypent-4-enoic acid] α-hydroxy acids. The use of (2S)-2-hydroxypent-4-enoic acid instead of a complex side-chain-protected hydrophilic building block obvi-

Reaction intermediate analogues as bisubstrate inhibitors of pantothenate synthetase

“…24 Protection of the resultant hydroxyl group as a TBS ether provided 8 , which was coupled with N -hydroxysuccinimide (NHS) using DCC to afford the common reaction intermediate 9 . The pantoyl-adenylate analogue 1a was then prepared by acylation of 2′,3′-isopropylidene-5′- O -(sulfamoyl)adenosine 10 25 with 9 employing Cs 2 CO 3 in DMF followed by concomitant deprotection of the TBS and acetonide groups using aqueous trifluoroacetic acid (TFA).…”

Precise Synthesis of Molecularly Defined Oligomers and Polymers by Orthogonal Iterative Divergent/Convergent Approaches

“…Surprisingly only two of the emerging robust, efficient and orthogonal click chemistries have been reported for the construction of molecularly defined oligomers via thiol-ene and CuAAC. [51,54] Taking into account the broad library of chemical reactions that satisfy the click chemistry philosophy, an astonishing array of potential IDC protocols for the development of molecularly defined and multifunctional oligomers is expected. The emergence of these perfectly defined oligomers and polymers will help develop structure property relationships and will have a broad scientific impact on many important industries.…”

“…(Scheme 27). [51] Therefore, reactive oligoester scaffolds with a precisely defined length and a strictly alternating sequence of hydrophobic (2S)-2-hydroxy-4-methylpentanoic acid (HMA) and masked hydrophilic (2S)-2-hydroxypent-4-enoic acid (HEA) were prepared using an IDC approach. Key intermediate orthogonally protected dimer 73 2 was prepared in three steps from HMA and HEA and included Thp ether and allyl ester groups to mask the hydroxy and carboxylic chain ends, respectively.…”

Rational Design and Synthesis of a Fluorinated Adenosine Derivative

“…化合物 1 的合成如 Scheme 2 所示: 以 D-叔亮氨酸 为原料, 采用文献报道的方法 [11] 将氨基转换为羟基得 化合物 2, 该反应中碳原子的手性保持. 化合物 2 经保 护、 酯化反应得中间体 4, 三步总产率 38%与文献 [7,11,12]相当; 以阿糖腺苷为原料, 经选择性保护 3'位和 5'位 羟基, 用二乙胺基三氟化硫(DAST)氟代得化合物 6.…”