(3S)-3-<(Benzyloxycarbonyl)amino>-1-oxaspiro<4.5>deca-7,10-diene-2,8-dione | 141406-16-8

• 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: (3S)-3-<(Benzyloxycarbonyl)amino>-1-oxaspiro<4.5>deca-7,10-diene-2,8-dione
• 英文别名: (S)-[(benzyloxycarbonyl)amino]-1-oxaspiro[4.5]deca-7,10-diene-2,8-dione；(S)-benzyl 2,8-dioxo-1-oxaspiro[4.5]deca-6,9-dien-3-ylcarbamate；(3S)-3-[(Benzyloxycarbonyl)amino]-1-oxaspiro[4.5]deca-7,10-diene-2,8-dione；benzyl N-[(3S)-2,8-dioxo-1-oxaspiro[4.5]deca-6,9-dien-3-yl]carbamate
• CAS: 141406-16-8
• 化学式: C₁₇H₁₅NO₅
• 分子量: 313.31
• InChiKey: PGKQZJADGOPNLL-AWEZNQCLSA-N

物化性质

• 沸点：
  599.5±50.0 °C(Predicted)
• 密度：
  1.35±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  81.7
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3S)-3-<(Benzyloxycarbonyl)amino>-1-oxaspiro<4.5>deca-7,10-diene-2,8-dione 在 platinum(IV) oxide 三乙烯二胺 、 咪唑 、 马来酸酐 、 盐酸 、 sodium tetrahydroborate 、 samarium diiodide 、 cerium(III) chloride 、 四丁基氟化铵 、 氢气 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 二苯醚 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 异丙醇 为溶剂， 230.0 ℃ 、101.33 kPa 条件下， 反应 194.33h， 生成 (1R,2R,2'S,2''E,3S,4R,4''E,6S,6''S,6''E,8''R,10''S,12''E,14''R)-1-[3'-tert-butyldiphenylsilyloxy-2'-(8'',10'',12'',14''-tetramethylhexadeca-2'',4'',6'',12''-tetraenoylamino)propyl]-2,3-epoxy-6-hydroxy-4-(4-methylbenzenesulfonyl)cyclohexan-1-ol
  参考文献：
  名称：

  （+）-Sphophostatin通过π-面部选择性Diels-Alder反应的立体选择性全合成

  摘要：

  描述了鞘磷脂抑制素的立体选择性全合成。亲水部分是通过（i）由l生成的螺内酯的高π面选择性Diels-Alder反应立体选择性合成的-酪氨酸和（ii）羟基指导的环氧化为关键反应。在最后阶段，将亲水性部分与疏水性侧链结合。通过小心执行轻度反应，克服了C5-C6环的不稳定性，实现了全合成。在这项工作的过程中，发现我们在先前的模型研究中错误地分配了最终产品C5-C6环氧环的相对立体化学。描述了模型研究中立体化学分配的修订。还合成了在C5和C6（环氧化物区域）的（+）-鞘磷脂抑制素异构体的非对映异构体。

  DOI：

  10.1021/jo070337k
• 作为产物：
  描述：

  N-苄氧羰基-L-酪氨酸 在 碘苯二乙酸 作用下， 以 甲醇 为溶剂， 以68%的产率得到(3S)-3-<(Benzyloxycarbonyl)amino>-1-oxaspiro<4.5>deca-7,10-diene-2,8-dione
  参考文献：
  名称：

  花粉生物碱的合成研究；酪氨酸的氧化环化立体选择性制备氢化吲哚环系统

  摘要：

  Stemona生物碱的核心氢吲哚环系是通过用高价碘试剂氧化酪氨酸，然后添加非对映异构基团选择性分子内共轭物来制备的。进一步的转化说明了高度官能化的氢化吲哚酮3在生物碱合成中的多功能性。

  DOI：

  10.1016/s0040-4039(00)61121-8

文献信息

• Development of new and efficient polymer-supported hypervalent iodine reagents
  作者：Simon Ficht、Marcel Mülbaier、Athanassios Giannis

  DOI：10.1016/s0040-4020(01)00424-0

  日期：2001.6

  The aminomethylpolystyrene-supported (diacetoxyiodo)benzene reagents 4a and 4b were prepared for the first time. Using these reagents several hydroquinones and phenols can be oxidized to the corresponding quinones. Spirocyclization of phenylacetic acid and of N-protected tyrosine derivatives could also be accomplished.

  首次制备了氨基甲基聚苯乙烯负载的（二乙酰氧基碘）苯试剂4a和4b。使用这些试剂，可以将几种氢醌和苯酚氧化为相应的醌。苯乙酸和N-保护的酪氨酸衍生物的螺环化也可以实现。
• Studies on the synthesis of Stemona alkaloids; stereoselective preparation of the hydroindole ring system by oxidative cyclization of tyrosine
  作者：Peter Wipf、Yuntae Kim

  DOI：10.1016/s0040-4039(00)61121-8

  日期：1992.9

  The core hydroindole ring system of the Stemona alkaloids was prepared by oxidation of tyrosine with a hypervalent iodine reagent followed by a diastereotopic group-selective intramolecular conjugate addition. Further transformations illustrate the versatility of the highly functionalized hydroindolenone 3 for alkaloid synthesis.

  Stemona生物碱的核心氢吲哚环系是通过用高价碘试剂氧化酪氨酸，然后添加非对映异构基团选择性分子内共轭物来制备的。进一步的转化说明了高度官能化的氢化吲哚酮3在生物碱合成中的多功能性。
• Total synthesis and structure assignment of the antitumor antibiotic aranorosin
  作者：Peter Wipf、Yuntae Kim、Paul C. Fritch

  DOI：10.1021/jo00077a050

  日期：1993.12

  The structurally unique antifungal and antitumor antibiotic aranorosin was prepared in a convergent, stereoselective sequence. Oxidative cyclization of N-protected L-tyrosine, followed by face-selective 1,2-addition of [(benzyloxy)methyl]lithium, Henbest oxidation in the presence of Kishi's radical inhibitor, and simultaneous N,O-deprotection led to an amino diol which was N-acylated with the fatty acid side-chain segment. After a low-temperature reduction of the lactone moiety to the lactol, the carbonyl function was regenerated under neutral conditions by diol cleavage with sodium periodate. Preparation of the acid side chain involved a diastereoselective imide alpha-alkylation directed by Evans' oxazolidinone auxiliary, followed by a series of Wittig-Horner chain extensions. Since the relative configuration at the C (6') position of the natural product had not been determined, we prepared both the (6'S) and the (6'R) isomers of aranorosin. Comparison of synthetic material with the reported spectral data for natural (-)-aranorosin, especially H-1 and C-13 NMR and [alpha]D, did not allow a definitive assignment. After purification of a sample of the isolated material from Pseudoarachniotus roseus, the corrected [alpha]D strongly indicated the (6'R)-stereochemistry for the natural compound. This assignment was confirmed by circular dichroism spectra for (6'S)- and (6'R)-aranorosin and the natural material.
• Synthesis of Hydroxylated Bicyclic Amino Acids from <scp>l</scp>-Tyrosine: Octahydro-1<i>H</i>-indole Carboxylates
  作者：Joshua G. Pierce、Dhanalakshmi Kasi、Makoto Fushimi、Anthony Cuzzupe、Peter Wipf

  DOI：10.1021/jo801552j

  日期：2008.10.3

  A stereoselective approach to polyhydroxylated L-Choi derivatives has been developed. The oxidative cyclization Of L-tyrosine was optimized to avoid partial racemization and to allow a more efficient scale-up.
• Stereoselective synthesis of the functionalized spirocyclic core of aranorosin
  作者：Peter Wipf、Yuntae Kim

  DOI：10.1021/jo00059a004

  日期：1993.3

  Oxidative cyclization of L-tyrosine, stereoselective addition of an alpha-alkoxy organolithium reagent, and hydroxyl-directed diepoxidation are key steps in the first synthesis of the fully functionalized core of aranorosin.