(R)-5-庚基二氢呋喃-2-酮 | 74568-06-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 中文名称: (R)-5-庚基二氢呋喃-2-酮
• 英文名称: (R)-5-heptyl-dihydrofuran-2-one
• 英文别名: (R)-5-heptyldihydrofuran-2(3H)-one；(R)-γ-undecalactone；(5R)-5-heptyloxolan-2-one
• CAS: 74568-06-2
• 化学式: C₁₁H₂₀O₂
• 分子量: 184.279
• InChiKey: PHXATPHONSXBIL-SNVBAGLBSA-N

物化性质

• LogP：
  2.961 (est)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-5-庚基二氢呋喃-2-酮 在 吡啶 、 三甲基铝 、 对甲苯磺酰氯 作用下， 以 正己烷 、 二氯甲烷 、 氯仿 为溶剂， 反应 2.0h， 生成 N-异丙基-p-乙烯基苯乙基胺
  参考文献：
  名称：

  Stereochemical Elucidation of Streptorubin B

  摘要：

  Streptorubin B is a structurally remarkable member of the prodiginine group of antibiotics produced by several actinobacteria, including the model organism Streptomyces coelicolor A3(2). Transannular strain within the pyrrolophane structure of this molecule causes restricted rotation that gives rise to the possibility of (diastereomeric) atropisomers. Neither the relative nor the absolute stereochemistry of streptorubin B is known. NOESY NMR experiments were used to define the relative stereochemistry of the major atropisomer of streptorubin B center dot HCl in solution as anti. We exploited this finding together with our knowledge of streptorubin B biosynthesis in S. coelicolor to determine the absolute stereochemistry of the anti atropisomer. 2-Undecylpyrrole stereoselectively labeled with deuterium at C-4' was synthesized and fed to a mutant of S. coelicolor, which was unable to produce streptorubin B because it was blocked in 2-undecylpyrrole biosynthesis, and in which the genes responsible for the last two steps of streptorubin B biosynthesis were overexpressed. H-1 and H-2 NMR analysis of the stereoselectively deuterium-labeled streptorubin B center dot HCl produced by this mutasynthesis strategy allowed us to assign the absolute stereochemistry of the major (anti) atropisomer as 7'S. HPLC analyses of streptorubin B isolated from S. coelicolor on a homochiral stationary phase and comparisons with streptorubin B derived from an enantioselective synthesis showed that the natural product consists of an approximately 88:7:5 mixture of the (7'S, anti), (7'S, syn), and (7'R, anti) stereoisomers.

  DOI：

  10.1021/ja109164t
• 作为产物：
  描述：

  (5S)-5-(hydroxymethyl)-2-oxo-tetrahydrofuran 在 吡啶 、 sodium 、 copper(l) cyanide 作用下， 以 四氢呋喃 、 正己烷 、 氯仿 为溶剂， 反应 9.75h， 生成 (R)-5-庚基二氢呋喃-2-酮
  参考文献：
  名称：

  Stereochemical Elucidation of Streptorubin B

  摘要：

  Streptorubin B is a structurally remarkable member of the prodiginine group of antibiotics produced by several actinobacteria, including the model organism Streptomyces coelicolor A3(2). Transannular strain within the pyrrolophane structure of this molecule causes restricted rotation that gives rise to the possibility of (diastereomeric) atropisomers. Neither the relative nor the absolute stereochemistry of streptorubin B is known. NOESY NMR experiments were used to define the relative stereochemistry of the major atropisomer of streptorubin B center dot HCl in solution as anti. We exploited this finding together with our knowledge of streptorubin B biosynthesis in S. coelicolor to determine the absolute stereochemistry of the anti atropisomer. 2-Undecylpyrrole stereoselectively labeled with deuterium at C-4' was synthesized and fed to a mutant of S. coelicolor, which was unable to produce streptorubin B because it was blocked in 2-undecylpyrrole biosynthesis, and in which the genes responsible for the last two steps of streptorubin B biosynthesis were overexpressed. H-1 and H-2 NMR analysis of the stereoselectively deuterium-labeled streptorubin B center dot HCl produced by this mutasynthesis strategy allowed us to assign the absolute stereochemistry of the major (anti) atropisomer as 7'S. HPLC analyses of streptorubin B isolated from S. coelicolor on a homochiral stationary phase and comparisons with streptorubin B derived from an enantioselective synthesis showed that the natural product consists of an approximately 88:7:5 mixture of the (7'S, anti), (7'S, syn), and (7'R, anti) stereoisomers.

  DOI：

  10.1021/ja109164t

文献信息

• Efficient Stereoselective Synthesis of Structurally Diverse γ‐ and δ‐Lactones Using an Engineered Carbonyl Reductase
  作者：Meng Chen、Xiao‐Yan Zhang、Chen‐Guang Xing、Chao Zhang、Yu‐Cong Zheng、Jiang Pan、Jian‐He Xu、Yun‐Peng Bai

  DOI：10.1002/cctc.201900382

  日期：2019.6.6

  efficiently synthesized stereoselectively using an engineered carbonyl reductase from Serratia marcescens (SmCRV4). SmCRV4 exhibited improved activity (up to 500‐fold) and thermostability toward 14 γ‐/δ‐keto acids and esters, compared with the wild‐type enzyme, with 110‐fold enhancement in catalytic efficiency (kcat/Km) toward methyl 4‐oxodecanoate. The preparative synthesis of alkyl and aromatic γ‐ and δ‐lactones

  结构结构多样的γ-和δ-内酯是利用粘质沙雷氏菌（Sm CR V4）中的一种工程化羰基还原酶有效地立体选择性合成的。与野生型酶相比，Sm CR V4表现出更高的活性（最高达500倍）和对14种γ-/δ-酮酸和酯的热稳定性，催化效率提高了110倍（k cat / K m）对4-氧代十二烷甲酸甲酯。证明了烷基和芳香族γ-和δ-内酯的制备合成，其ee率为95％-> 99％，收率为78％-90％。最高时空产量为1175 g L -1  d -1，达到了（R）-γ-癸内酯
• Stereoselective synthesis of chiral δ-lactones <i>via</i> an engineered carbonyl reductase
  作者：Tao Wang、Xiao-Yan Zhang、Yu-Cong Zheng、Yun-Peng Bai

  DOI：10.1039/d1cc04542c

  日期：——

  A carbonyl reductase variant, SmCRM5, from Serratia marcescens was obtained through structure-guided directed evolution. The variant showed improved specific activity (U mg−1) towards most of the 16 tested substrates and gave high stereoselectivities of up to 99% in the asymmetric synthesis of 13 γ-/δ-lactones. In particular, SmCRM5 showed a 13.8-fold higher specific activity towards the model substrate

  来自粘质沙雷氏菌的羰基还原酶变体Sm CR M5是通过结构引导的定向进化获得的。该变体对 16 种测试底物中的大多数表现出改善的比活性 (U mg -1 )，并在 13 种 γ-/δ-内酯的不对称合成中提供高达 99% 的高立体选择性。特别是，SmCR M5对模型底物（即5-氧代癸酸）的比活性高出 13.8 倍，并在 99% ee 中产生 ( R )-δ-癸内酯，时空产率 (STY) 为 301 g L -1 d -1. 六种δ-内酯的高收率和高对映体纯度的制备表明这些高附加值化学品的生物催化合成是可行的，为贵金属催化提供了一种具有成本效益的绿色替代品。
• Carboxyl Group-Directed Iridium-Catalyzed Enantioselective Hydrogenation of Aliphatic γ-Ketoacids
  作者：Mao-Lin Li、Yao Li、Jia-Bin Pan、Yi-Hao Li、Song Song、Shou-Fei Zhu、Qi-Lin Zhou

  DOI：10.1021/acscatal.0c02142

  日期：2020.9.4

  occurrence of chiral induction involving a hydrogen–hydrogen interaction between a hydride on the iridium atom and the substituent on the oxazoline ring of the ligand, and on the basis of the calculations, we proposed a catalytic cycle involving only Ir(III), which differs from the Ir(III)/Ir(V) catalytic cycle that operates in the hydrogenation of α,β-unsaturated carboxylic acids.

  尽管已经广泛地研究了过渡金属催化的芳族酮的不对称氢化，但是脂肪族酮的对映选择性氢化仍然是一个挑战，因为手性催化剂不能轻易地区分这些酮的正反面。在这里，我们报道了脂肪族γ-酮酸不对称氢化的羧基导向策略。在具有手性螺膦-恶唑啉配体的铱配合物的催化下，脂肪族γ-酮酸的氢化得到具有高对映选择性（高达99％ee）的手性γ-羟基内酯。机理研究表明，底物的羧基指导氢转移并确保高对映选择性。
• Stereoselective allylation of aldehydes on solid support and its application in biology-oriented synthesis (BIOS)
  作者：Victor Mamane、Ana B. García、Jayant D. Umarye、Torben Lessmann、Stefan Sommer、Herbert Waldmann

  DOI：10.1016/j.tet.2007.01.041

  日期：2007.6

  allylation of aldehydes on solid support is reported. Different kinds of chiral allylboron reagents with complementary direction of stereoinduction were applied successfully in this reagent-controlled transformation. The homoallylic alcohol products are generated with high levels of stereoselectivity and in high yields. The crotylation of aldehydes on solid support employing (E)- and (Z)-Ipc2crotylborane

  报道了在固体载体上醛的不对称烯丙基化的系统研究。具有立体诱导互补方向的不同种类的手性烯丙基硼试剂已成功应用于该试剂控制的转化中。均丁醇产物以高水平的立体选择性和高产率产生。使用（E）-和（Z）-Ipc 2在固相载体上醛的crotylation。巴豆基硼烷还以很高的立体诱导水平和高收率进行。描述了该方法在通过烯丙基部分的后续修饰来合成化合物集合中的应用。特别地，已经通过包括天然产物的环释放方法合成了γ-和δ-内酯的集合。另外，已经报道了解决固体载体上双键的长期存在问题的方法。我们还证明了以迭代方式在固体载体上应用醛的立体选择性烯丙基化以生成多元醇结构的可行性。
• Facile Synthesis of Optically Active .GAMMA.-Lactones via Lipase-catalyzed Reaction of 4-Substituted 4-Hydroxybutyramides.
  作者：Yassufumi MATSUMURA、Teruko ENDO、Mituo CHIBA、Hidemichi FUKAWA、Yoshiyasu TERAO

  DOI：10.1248/cpb.48.304

  日期：——

  afford (S)-succinic acid monoester and unreacted (R)-4-hydroxybutyramide derivative, which were separated easily by treatment with an alkaline solution. Both enantiomers were converted easily to optically active gamma-substituted gamma-butyrolactones.

  外消旋的4-取代的4-羟基丁酰胺与琥珀酸酐的脂肪酶催化的酯交换反应对映选择性地进行，得到（S）-琥珀酸单酯和未反应的（R）-4-羟基丁酰胺衍生物，通过用碱溶液处理容易地分离它们。两种对映异构体均易于转化为光学活性的γ-取代的γ-丁内酯。