tert-butyl N-benzenesulfonyl-(S)-pyroglutamate | 378238-37-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: tert-butyl N-benzenesulfonyl-(S)-pyroglutamate
• 英文别名: t-butyl N-(phenylsulfonyl)pyroglutamate
• CAS: 378238-37-0
• 化学式: C₁₅H₁₉NO₅S
• 分子量: 325.386
• InChiKey: ODWQBAKYNVOIRX-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.71
• 重原子数：
  22.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  80.75
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  tert-butyl N-benzenesulfonyl-(S)-pyroglutamate 在 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 41.0h， 生成 1-Allyl-9-((S)-1-benzenesulfonyl-5-oxo-pyrrolidine-2-carbonyl)-1,9-dihydro-β-carboline-2-carboxylic acid 2,2,2-trichloro-ethyl ester
  参考文献：
  名称：

  A general method for the asymmetric synthesis of both enantiomers of 1-substituted 1,2,3,4-tetrahydro-β-carbolines employing pyroglutamic acid derivatives as chiral auxiliaries

  摘要：

  9-(S)-Pyroglutaminyl-beta-carbolines were allowed to react with a nucleophile (allyltributyltin or a silyl enol ether) in the presence of 2,2,2-trichloroethyl chloroformate to give 1,2-addition products in good yields and high diastereoselectivity. The chiral auxiliary at N-9 was readily removed by a mild hydrolysis. The same chiral source afforded both enantiomers by simply altering a protecting group of the amide nitrogen. That is, (S)-pyroglutaminyl groups which had an N-alkyl group afforded the (S) isomer, whereas the ones having an N-acyl group produced the (R) isomer of the addition products. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)00420-4
• 作为产物：
  描述：

  醋酸叔丁酯 在 高氯酸 、 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 48.5h， 生成 tert-butyl N-benzenesulfonyl-(S)-pyroglutamate
  参考文献：
  名称：

  (+)-asperazine A 的全合成：立体选择性多米诺二聚

  摘要：

  (+)-asperazine A 的简明全合成，具有不对称的 C3-N1' 键，通过前所未有的基于 4 N的级联连接立体选择性地实现。从亲核苯胺 (N 1 ) 到亲电N-碘苯胺的转化是通过氧化剂碘阳离子实现的，通过 1,3-二羰基碘甲基环丙烷的 Ni 催化酮/烯醇互变异构开环稳定释放。它通过烯胺 (N 2 ) 的内切攻击引发缩合，然后添加苯胺 (N 3 ) 以在 C3 位置进行关键季铵化。在第一次环化中产生的质子引发了烯胺的异构现象（N 4) 到 iminium，然后从苯胺 (N 1 )添加。不对称二聚体4是通过由吲哚芳构化的热力学稳定性驱动的开环 (N 4 )获得的。这个多米诺骨牌过程依次组装四个不同的“N”，以实现苯胺-二氢-吡咯二聚-异构化，有效地建立了一个由 22 个成员组成的阿斯哌嗪 A 支架库。对照实验和密度泛函理论计算支持亲电子N-碘苯胺途径并阐明了高度内切选择性偏好。

  DOI：

  10.1016/j.chempr.2022.10.021

文献信息

• Preparation of both enantiomers of 1-allyl-1,2,3,4-tetrahydro-β-carboline using allyltin reagents and a chiral auxiliary derived from l-proline
  作者：Takashi Itoh、Yûji Matsuya、Yasuko Enomoto、Akio Ohsawa

  DOI：10.1016/s0040-4020(01)00684-6

  日期：2001.8

  beta -Carboline, which had an acyl group derived from L-proline at the 9-position, reacted with allyltributyltin and 2,2,2-trichloroethyl chloroformate, to afford an 1-allyl-1,2-dihydro-beta -carboline derivative in a diastereo selective manner. The chiral acyl group at N-9 was readily eliminated by aqueous alkali to give a corresponding carboxylic acid. The formed 1-allyl-1,2-dihydro-beta -carboline was transformed via two reduction steps to 1-alkyl-1,2,3,4-tetrahydro-beta -carboline in high ee. When the allylation was carried out using tetraallyltin instead of allyltributyltin, the stereoselectivity was reversed, and the antipode of the allyl adduct was obtained in high yield and ee in the presence of tin(IV) tetraiodide. Thus, it was found that both enantiomers of 1-allyl-beta -carboline were obtained in good enantioselectivities by the use of the same chiral auxiliary. (C) 2001 Elsevier Science Ltd. All rights reserved.