(4RS,5RS)-4-hydroxy-5-methyldihydrofuran-2(3H)-one | 38996-22-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (4RS,5RS)-4-hydroxy-5-methyldihydrofuran-2(3H)-one
• 英文别名: 4r-hydroxy-5c-methyl-dihydro-furan-2-one；DL-threo-2,5-dideoxy-pentonic acid 4-lactone；InChI=1/C5H8O3/c1-3-4(6)2-5(7)8-3/h3-4,6H,2H2,1H3/t3-,4-/m0/s；(4S,5S)-4-hydroxy-5-methyloxolan-2-one
• CAS: 38996-22-4
• 化学式: C₅H₈O₃
• 分子量: 116.117
• InChiKey: BYSKAPIRGIONBO-IMJSIDKUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4RS,5RS)-4-hydroxy-5-methyldihydrofuran-2(3H)-one 在 甲基磺酰氯 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以87%的产率得到(S)-(+)-β-angelica lactone
  参考文献：
  名称：

  Brief syntheses of (+)-blastmycinone and related γ-lactones from an asymmetrically dihydroxylated carboxylic ester

  摘要：

  A method for synthesizing optically active trans,trans-configurated alpha,beta,gamma-substituted gamma-lactones is presented. Asymmetric hydroxylation of ester 8 with AD mix alpha (AD mix beta) and subsequent dehydration provided butenolide S-6 (R-6). Conjugate addition of Li-2(Me2PhSi)(2)Cu(CN) to S-6 followed by alkylation of the resulting enolate led to the stereopure silyllactones 9-11. They furnished the title compounds after oxidative removal of the Me2PhSi group. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00687-5
• 作为产物：
  描述：

  methyl (E)-pent-3-enoate 在 AD-mix-α 作用下， 以 水 、 叔丁醇 为溶剂， 反应 240.0h， 以47%的产率得到(4RS,5RS)-4-hydroxy-5-methyldihydrofuran-2(3H)-one
  参考文献：
  名称：

  Brief syntheses of (+)-blastmycinone and related γ-lactones from an asymmetrically dihydroxylated carboxylic ester

  摘要：

  A method for synthesizing optically active trans,trans-configurated alpha,beta,gamma-substituted gamma-lactones is presented. Asymmetric hydroxylation of ester 8 with AD mix alpha (AD mix beta) and subsequent dehydration provided butenolide S-6 (R-6). Conjugate addition of Li-2(Me2PhSi)(2)Cu(CN) to S-6 followed by alkylation of the resulting enolate led to the stereopure silyllactones 9-11. They furnished the title compounds after oxidative removal of the Me2PhSi group. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00687-5

文献信息

• Total Syntheses of Carbohydrates, IV. 2-Deoxy-DL-, L- and D-<i>erythro</i>-pentoses and Related Sugars
  作者：Gen Nakaminami、Sachiko Shioi、Yoko Sugiyama、Satoko Isemura、Mikio Shibuya、Masazumi Nakagawa

  DOI：10.1246/bcsj.45.2624

  日期：1972.8

  5-dideoxy-threo-pentono-γ-lactone (III) could be obtained stereoselectively from 3-hydroxy-4-pentenoic acid (I) by the reaction with N-bromosuccinimide in water. On successive treatment with an aqueous potassium hydroxide and an acid type cation exchange resin, bromolactone (III) gave stereoselectively 2-deoxy-erythro-pentono-γ-lactone (IV). Reduction of IV by means of bis(1,2-dimethylpropyl)borane afforded

  5-Bromo-2,5-dideoxy-threo-pentono-γ-lactone (III) 可以立体选择性地从 3-hydroxy-4-pentenoic acid (I) 与 N-bromosuccinimide 在水中反应获得。在用氢氧化钾水溶液和酸型阳离子交换树脂连续处理后，溴内酯 (III) 得到立体选择性的 2-脱氧-赤型-戊酮-γ-内酯 (IV)。通过双(1,2-二甲基丙基)硼烷还原IV，得到2-脱氧-赤型-戊糖(V)。3-Hydroxy-4-pentenoic acid (I) 可以被光学拆分。(+)-酸产生2-脱氧-D-赤型-戊糖(DV)，(-)-酸可转化为2-脱氧-L-赤型-戊糖(LV)。2,5-Dideoxy-threo-pentose (VIII) 和 5-bromo-2,5-dideoxy-threo-pentose (IX) 从溴内酯 (III) 中获得。
• Elucidation of the stereostructure of the annonaceous acetogenin (+)-montecristin through total synthesis
  作者：Christian Harcken、Reinhard Brückner

  DOI：10.1039/b002905j

  日期：——

  Total syntheses of ent-5-epi-montecristin (1a) and of (−)-montecristin (1b) were accomplished. The stereocenters of compounds 1a and 1b were established by asymmetric dihydroxylations of the trans-configurated β,γ-unsaturated esters 6 ( → 4, up to 80% ee; Scheme 3; improved procedure with up to 94% ee: Scheme 7) and 56 ( → 55, 97% ee: Scheme 9) while the stereogenic CC bonds stem from the carbocuprations

  完成了ent -5- epi- montecristin（1a）和（-）-montecristin（1b）的总合成。化合物1a和1b的立体中心是通过反式构型的β，γ-不饱和酯6的不对称二羟基化而建立的（→ 4，至多80％ee；方案3；改进的程序，至多94％ee：方案7）和56（→ 55，97％ee的：方案9），而立体ç C键从carbocuprations干48 → 49和50 → 51（方案9）。用PPh 3和DEAD处理羟基内酯27（方案7）， 3a（方案12）和3b（方案13），我们发现无外消旋的脱水作用生成丁烯内酯26，无差向异构化的脱水作用生成丁烯内酯2a和2b 。有关的[ α ] d合成的值 1A和1B到[ α ] d天然（+）的值- montecristin，测定其侧链立体中心的绝对构型为[R 。
• Marliolide inhibits skin carcinogenesis by activating NRF2/ARE to induce heme oxygenase-1
  作者：June Lee、Karabasappa Mailar、Ok-Kyung Yoo、Won Jun Choi、Young-Sam Keum

  DOI：10.1016/j.ejmech.2018.02.068

  日期：2018.4

  catalyzes the enzymatic degradation of heme to produce three anti-oxidant molecules: carbon monoxide (CO), ferrous ion (Fe2+), and biliverdin. Induction of HO-1 is currently considered as a feasible strategy to treat oxidative stress-related diseases. In the present study, we identified marliolide as a novel inducer of HO-1 in human normal keratinocyte HaCaT cells. Mechanism-based studies demonstrated

  血红素加氧酶-1（HO-1）催化血红素的酶促降解，产生三种抗氧化剂分子：一氧化碳（CO），亚铁离子（Fe 2+）和biliverdin。HO-1的诱导目前被认为是治疗氧化应激相关疾病的可行策略。在本研究中，我们确定了马里利利德是人正常角质形成细胞HaCaT细胞中HO-1的新型诱导剂。基于机理的研究表明，马里内酯对HO-1的诱导是通过马里内利德与KEAP1的直接结合，通过激活NRF2 / ARE来实现的。构效关系揭示了对HO-1的诱导至关重要的马里里利德的化学部分，这为迈克尔反应作为一种潜在的作用机理提供了支持。最后，我们观察到马里立内酯在DMBA / TPA诱导的小鼠皮肤癌变模型中显着抑制了乳头状瘤的形成，并且该事件与体内降低8-OH-G和4-HNE的形成密切相关。在一起，我们的研究提供了第一个证据，证明马里利内酯可能有效治疗与氧化应激相关的皮肤疾病。
• 말리올라이드 유도체를 유효성분으로 함유하는 항산화용 조성물
  申请人：TAENAM MEDICOS CO.,LTD 태남메디코스 주식회사(120150309951) Corp. No ▼ 154511-0061608BRN ▼303-81-77538

  公开号：KR102007282B1

  公开（公告）日：2019-08-06

  본 발명은 말리올라이드 유도체 및 이를 유효성분으로 함유하는 항산화용 조성물에 관한 것으로, 상기 말리올라이드 유도체는 세포독성 없이 항산화관련 단백질의 발현을 조절하는 전사인자 Nrf2의 발현을 증가시킴으로써, 항산화 관련 단백질인 HO-1 및 NQO1의 발현을 증가시켰으며, 산화적 스트레스를 유발시키는 TPA에 의해 유도된 DNA 및 지질의 산화를 억제하는 것으로 확인됨에 따라, 상기 말리올라이드 유도체를 유효성분으로 함유하는 조성물은 항산화용 조성물로 제공될 수 있다.

  本发明涉及马里奥酰胺衍生物及其作为有效成分含有抗氧化剂的组合物，所述马里奥酰胺衍生物通过增加转录因子Nrf2的表达来调节抗氧化相关蛋白的表达，而无细胞毒性，增加了抗氧化相关蛋白HO-1和NQO1的表达，并且通过抑制由TPA诱导的DNA和脂质氧化，确认其抑制氧化应激。因此，含有上述马里奥酰胺衍生物作为有效成分的组合物可作为抗氧化剂组合物提供。
• Enantiomeric β-angelica lactone epoxides: their syntheses from suitable chiral precursors and their use in the preparation of blastmycinone
  作者：Rosa M. Ortuño、Daniel Alonso、Jaume Cardellach、Josep Font

  DOI：10.1016/s0040-4020(01)86801-0

  日期：1987.1

  Syntheses of (S)-β-angelica lactone from L-tartaric acid and (R)-γ-hydroxy-methyl-γ-butyrolactone, 5, are reported. Alternative routes to prepare 5 from S- and R-glutamic acids and D-ribonolactone, respectively, are also presented. Epoxides derived from (R)- and (S)-β-angelica lactones have been obtained and their use in the synthesis of both (+)- and (-)-blastmycinone, 24, has been established.

  报道了由L-酒石酸和（R）-γ-羟基-甲基-γ-丁内酯5合成（S）-β-当归内酯。还提出了分别由S-，R-谷氨酸和D-核糖内酯制备5的替代方法。已经获得了衍生自（R）-和（S）-β-当归内酯的环氧化物，并且已经确定了它们在合成（+）-和（-）-blastmycinone（24）中的用途。

表征谱图