N_α-benzyloxycarbonyl-L-lysine benzyl ester p-toluenesulfonate | 5361-91-1

• 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: N_α-benzyloxycarbonyl-L-lysine benzyl ester p-toluenesulfonate
• 英文别名: benzyl N(α)-(benzyloxycarbonyl)lysinate p-toluenesulfonate；Nα-Carbobenzoxy-L-lysine benzyl ester p-toluenesulfonate；Z-Lys-OBn*TsOH；N^α-Benzyloxycarbonyl-L-lysin-benzylester；Z-L-Lysine benzyl ester 4-toluenesulfonate salt；benzyl (2S)-6-amino-2-(phenylmethoxycarbonylamino)hexanoate;4-methylbenzenesulfonic acid
• CAS: 5361-91-1
• 化学式: C₇H₈O₃S*C₂₁H₂₆N₂O₄
• 分子量: 542.653
• InChiKey: PERBHXHGFSEBTK-FYZYNONXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  38
• 可旋转键数：
  13
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  153
• 氢给体数：
  3
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  N_α-benzyloxycarbonyl-L-lysine benzyl ester p-toluenesulfonate 在 18-冠醚-6 sodium cyanoborohydride 、 sodium carbonate 作用下， 以 乙腈 为溶剂， 反应 0.5h， 生成 (2S,9R)-7-Benzyl-2-(carbobenzoxyamino)-10-cyano-9-hydroxy-7-azadecanoic acid benzyl ester
  参考文献：
  名称：

  Total syntheses of (+)-hypusine and its (2S,9S)-diastereomer

  摘要：

  The total synthesis of (2S,9R)-hypusine dihydrochloride, an unusual amino acid constituent of the eukaryotic translation initiation factor eIF-4D, and its (2S,9S) diastereomer is described. The key step in the syntheses involves the Nepsilon-alkylation of Nepsilon-benzyl-Nalpha-(L)-lysine benzyl ester with (R)- or (S)-epichlorohydrin to give the respective (2S,9R) and (2S,9S) chlorohydrins. Subsequent displacement of the respective chlorides by cyanide ion provides the protected hypusine skeletons. The final step, hydrogenation over PtO2 in AcOH followed by neutralization and reacidification, yielded the respective (2S,9S)- and (2S,9R)-hypusine dihydrochlorides in excess of 50% overall yield.

  DOI：

  10.1021/jo00076a048
• 作为产物：
  描述：

  N-alpha-Cbz-L-赖氨酸 、 对甲苯磺酸 、 水 、 对甲苯磺酸一水合物 在 乙醚 作用下， 以 苯甲醇 、 甲苯 为溶剂， 以to afford 12 g (62%) of the title compound, ν (Nujol) 3370, 1735, 1692, 1040, 1015, 820, 745, 735, 700, 685 cm-1的产率得到N_α-benzyloxycarbonyl-L-lysine benzyl ester p-toluenesulfonate
  参考文献：
  名称：

  A-deoxy-a-aza derivatives of clavulanic acid, a process for their

  摘要：

  化学式（II）的化合物：##STR1## 或其药学上可接受的盐或酯，其中A是氢原子或酯化基团；X是1-12个碳原子的烷基，可选地被氢氧基，氨基，C.sub.1-6酰胺基或C.sub.1-6烷氧基取代，这些取代基不在氮原子相邻的碳原子上；或C.sub.5-7环烷基；或苯基烷基，其中烷基部分的碳原子含量为1-6，苯基部分可选地被氟，溴，氯，C.sub.1-6烷基或C.sub.1-6烷氧基取代；但是当X表示可选地取代的苯基烷基且A表示C.sub.1-3烷基时，-CO.sub.2 A基团附加在苯基烷基的烷基部分上；已被发现是β-内酰胺酶抑制剂和抗菌剂。它们的制备和使用被描述了。

  公开号：

  US04652560A1

文献信息

• Synthesis and Stereochemistry of Hypusine, a New Amino Acid in Bovine Brain.
  作者：Tetsuo Shiba、Hitoshi Akiyama、Isao Umeda、Satoshi Okada、Tateaki Wakamiya

  DOI：10.1246/bcsj.55.899

  日期：1982.3

  Hypusine, a new basic amino acid occurring in the homogenate of bovine brain tissue, was synthesized to determine the absolute structure. Nα-Benzyloxycarbonyl-l-lysine benzyl ester was coupled with (S)- or (R)-4-benzyloxycarbonylamino-1-bromo-2-butanol derived from l- or d-malic acid, respectively. The products were deprotected by catalytic hydrogenation. One of the synthetic compounds, i.e., (2S,9R)-2,11-diamino-9-hydroxy-7-azaundecanoic acid, was completely identical with natural hypusine in all respects.

  羟脯氨酸是一种新发现的基本氨基酸，存在于牛脑组织的匀浆中，为了确定其绝对结构，进行了合成。Nα-苄氧基碳基-L-赖氨酸苄基酯与(S)-或(R)-4-苄氧基碳酰氨基-1-溴-2-丁醇（分别源自L-或D-苹果酸）偶联。合成产物通过催化氢化去保护。其中一种合成化合物，即(2S,9R)-2,11-二氨基-9-羟基-7-氮杂十一酸，在各方面与天然羟脯氨酸完全相同。
• Derivatives of clavulanic acid, a process for their preparation and
  申请人：Beecham Group p.l.c.

  公开号：US04539202A1

  公开（公告）日：1985-09-03

  The compounds of the formula (II): ##STR1## or pharmaceutically acceptable salts or esters thereof wherein A is a hydrogen atom or an esterifying radical; X is an alkyl group of 1-12 carbon atoms optionally substituted by a hydroxy, amino, acylamino of C.sub.1-6 alkoxy group, which substituents are not on the carbon atom adjacent to the nitrogen atom; or a C.sub.5-7 cycloalkyl group; or a phenylalkyl group wherein the carbon atom content of the alkyl part is 1-6 and the phenyl part is optionally substituted with a fluorine, bromine, chlorine, C.sub.1-6 alkyl, or C.sub.1-6 alkoxy; with the proviso that when X represents an optionally substituted phenylalkyl group and A represents C.sub.1-3 alkyl, then the --CO.sub.2 A group is attached to the alkyl part of the phenylalkyl group; have been found to be .beta.-lactamase inhibitors and antibacterial agents. Their preparation and use is described.

  化学式为(II)的化合物：##STR1## 或其药学上可接受的盐或酯，其中A是氢原子或酯化基团；X是1-12碳原子的烷基，可选择地被氢氧基，氨基，C.sub.1-6酰胺基或C.sub.1-6烷氧基取代，这些取代基不在与氮原子相邻的碳原子上；或是C.sub.5-7环烷基；或是苯基烷基，其中烷基部分的碳原子含量为1-6，苯基部分可选择地被氟，溴，氯，C.sub.1-6烷基或C.sub.1-6烷氧基取代；但是当X代表可选择地被取代的苯基烷基且A代表C.sub.1-3烷基时，--CO.sub.2 A基团附着在苯基烷基的烷基部分上；这些化合物被发现是β-内酰胺酶抑制剂和抗菌剂。它们的制备和使用被描述。
• Synthesis and Antitumor Activity of Conjugates of Muramyldipeptide, Normuramyldipeptide, and Desmuramylpeptides with Acridine/Acridone Derivatives
  作者：Krystyna Dzierzbicka、Aleksander M. Kołodziejczyk、Barbara Wysocka-Skrzela、Andrzej Myśliwski、Danuta Sosnowska

  DOI：10.1021/jm001115g

  日期：2001.10.1

  The synthesis of two groups (Chart 1, types A and B) of conjugates of MDP (muramyldipeptide) and nor-MDP (normurainyldipeptide) with acridine/acridone derivatives and the synthesis of analogues of desmuramylpeptides (Chart 1, types C and D), containing acridine/ acridone derivatives have been described. In type A conjugates, the hydroxyl group at C6 of the sugar moiety was acylated with acridine/acridone N-substituted omega -aminoalkanocarboxylic acids (Scheme 1), whereas the conjugates of type B (Table 2) and three analogues of type C or D (Scheme 2) have an amide bond formed between the carboxylic group of isoglutamine and the amine function of the respective acridine/acridone derivatives. The preliminary screening data indicate that the analogues of groups A, C, and D exhibit small cytotoxic activity, whereas several analogues of type B, 4b, 4c, 4e, 4g, 4h, 4i, and 4l, exhibiting potent in vitro cytotoxic activity against a panel of human cell lines (Table 4), have been selected by the National Cancer Institute (NCI) Evaluation Committee for further testing. Analogues 4b and 4h were active in the in vivo hollow fiber assay (Table 5). Analogue 3a shows an immunostimulating effect on the cytotoxic activity of the NX cells obtained from the spleen of healthy and Ab melanoma bearing animals.
• Synthesis of hypusine and other polyamines using dibenzyltriazones for amino protection
  作者：Spencer Knapp、Jeffrey J. Hale、Margarita Bastos、Audrey Molina、Kuang Yu Chen

  DOI：10.1021/jo00049a036

  日期：1992.11

  The use of 1,3-dibenzyl-5-substituted-hexahydro-2-oxo-1,3,5-triazine ("dibenzyltriazone") as a protecting group for primary amino is described. Optimized conditions for formation and hydrolysis of dibenzyltriazones, as well as a variety of transformations (reduction, oxidation, hydroxyl modification, C-C bond formation) compatible with this protecting group, are presented. N-Protected amino aldehydes such as 46, 47, and 94 are particularly valuable building blocks, as demonstrated by the syntheses of hypusine (86), deoxyhypusine (85), spermidine (74), and two unsaturated spermidine analogues 81 and 84.
• Total syntheses of (+)-hypusine and its (2S,9S)-diastereomer
  作者：Raymond J. Bergeron、Michael X. B. Xia、Otto Phanstiel

  DOI：10.1021/jo00076a048

  日期：1993.11

  The total synthesis of (2S,9R)-hypusine dihydrochloride, an unusual amino acid constituent of the eukaryotic translation initiation factor eIF-4D, and its (2S,9S) diastereomer is described. The key step in the syntheses involves the Nepsilon-alkylation of Nepsilon-benzyl-Nalpha-(L)-lysine benzyl ester with (R)- or (S)-epichlorohydrin to give the respective (2S,9R) and (2S,9S) chlorohydrins. Subsequent displacement of the respective chlorides by cyanide ion provides the protected hypusine skeletons. The final step, hydrogenation over PtO2 in AcOH followed by neutralization and reacidification, yielded the respective (2S,9S)- and (2S,9R)-hypusine dihydrochlorides in excess of 50% overall yield.