(4R,5R)-1,2,3,4,5-penta-O-acetyl-1-C-(1,2-dimethyl-4-nitrocyclohex-1-en-5-yl)-D-manno-pentitol | 438625-50-4

• 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: (4R,5R)-1,2,3,4,5-penta-O-acetyl-1-C-(1,2-dimethyl-4-nitrocyclohex-1-en-5-yl)-D-manno-pentitol
• 英文别名: 1',2',3',4',5'-penta-O-acetyl-1'-C-[(4R,5R)-1,2-dimethyl-4-nitrocyclohex-1-en-5-yl]-D-manno-pentitol；[(2R,3R,4R,5R)-2,3,4,5-tetraacetyloxy-5-[(1R,6R)-3,4-dimethyl-6-nitrocyclohex-3-en-1-yl]pentyl] acetate
• CAS: 438625-50-4
• 化学式: C₂₃H₃₃NO₁₂
• 分子量: 515.515
• InChiKey: YGOGWWLWEGXNNP-YTAOHXRWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  36
• 可旋转键数：
  15
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  177
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  (4R,5R)-1,2,3,4,5-penta-O-acetyl-1-C-(1,2-dimethyl-4-nitrocyclohex-1-en-5-yl)-D-manno-pentitol 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 苯 为溶剂， 反应 2.0h， 以27%的产率得到Acetic acid (1R,2R,3R)-2,3,4-triacetoxy-1-[(R)-acetoxy-((S)-3,4-dimethyl-cyclohex-3-enyl)-methyl]-butyl ester
  参考文献：
  名称：

  Stereoselective denitrohydrogenation reactions of 4-alkyl-5-glyco-4-nitrocyclohex-1-enes

  摘要：

  The denitrohydrogenation of chiral 4-alkyl-5-glyco-4-nitrocyclohex-1-enes (1 and 3) with tri-n-butyltin hydride and azobisisobutironitrile proceeded in a completely stereoselective way. In each case. the hydrogen atom provided by tri-n-butyltin hydride adds to a free radical intermediate in a trans mode to the adjacent, sterically demanding, sugar side-chain. Attempts to perform denitroalkylation reactions of 1a, 3a or 8 with electron-deficient alkenes yielded only denitrohydrogenated products. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00304-4
• 作为产物：
  描述：

  (E)-3,4,5,6,7-penta-O-acetyl-1,2-dideoxy-1-C-nitro-D-manno-hept-1-enitol 、 2,3-二甲基-1,3-丁二烯 以 甲苯 为溶剂， 以10%的产率得到(4S,5S)-1,2,3,4,5-penta-O-acetyl-1-C-(1,2-dimethyl-4-nitrocyclohex-1-en-5-yl)-D-manno-pentitol
  参考文献：
  名称：

  Serrano, Jose A.; Moreno, Maria Ch.; Roman, Emilio, Journal of the Chemical Society. Perkin transactions I, 1991, # 12, p. 3207 - 3212

  摘要：

  DOI：

文献信息

• Reactions of hydroxylated sodium nitronates with acetic anhydride/pyridine
  作者：M.V Berrocal、M.V Gil、E Román、J.A Serrano

  DOI：10.1016/s0040-4020(02)00487-8

  日期：2002.6

  Reactions with Ac2O/Py of sodium nitronate salts derived from primary or secondary nitroalkanes bearing hydroxyl groups at γ or more remote positions have been studied. In all cases, the results could be explained through an acetic nitronic anhydride intermediate, whose evolution depends on conformational factors, and also on the type of the hydroxyl group.

  已经研究了由γ或更远的位置带有羟基的伯或仲硝基烷烃衍生的亚硝酸钠盐与Ac 2 O / Py的反应。在所有情况下，结果都可以通过乙酸乙酸酐中间体来解释，该中间体的演变取决于构象因素，还取决于羟基的类型。
• Stereoselective Michael addition reactions of 5-glyco-4-nitrocyclohex-1-enes
  作者：P. Areces、M.V. Gil、F.J. Higes、E. Román、J.A. Serrano

  DOI：10.1016/s0040-4039(98)01911-x

  日期：1998.11

  Michael additions of 5-glyco-4-nitrocyclohex-1-enes (2 and 3) proceeded in a stereoselective way, leading in each case to single adducts in which the electron-deficient alkenes add on the C-4 of the cyclohexene rings, in a trans mode to the adjacent, sterically demanding, sugar side-chain. When dimethyl maleate or dimethyl fumarate and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) were used, there was in

  5-糖基-4-硝基环己基-1-烯（2和3）的迈克尔加成反应以立体选择性方式进行，在每种情况下都导致单个加合物，其中缺电子的烯烃在环己烯环的C-4上加成，以反式模式连接到相邻的，空间要求高的糖侧链。当使用马来酸二甲酯或富马酸二甲酯和1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）时，就地消除了亚硝酸，产物由1：1的差向异构体混合物组成α，β-不饱和酯7。
• Preparation of enantiomerically pure 4-alkyl-5-formyl-4-nitrocyclohex-1-enes from 5-glyco-4-nitrocyclohex-1-enes
  作者：R. Ballini、G. Bosica、M.V. Gil、E. Román、J.A. Serrano

  DOI：10.1016/s0957-4166(02)00416-0

  日期：2002.8

  electron-deficient alkenes yielded, in all cases, adducts in which the sugar side-chain and the added group on C-4 of the cyclohexene ring showed a trans-relationship. Furthermore, some of the adducts have been used to prepare enantiomerically pure 4-alkyl-5-formyl-4-nitrocyclohex-1-enes by a two-step process involving base-catalyzed (NaOMe) deacetylation of their respective sugar side-chains and subsequent

  在所有情况下，碱催化（TMG，DBU或TEA）在5-glyco-4-nitrocyclohex-1-enes 1a或1b与许多单或α，β-di取代的缺电子烯烃之间的不对称Michael反应，加合物，其中所述糖侧链和添加的组上C-4的环己烯环的呈反式-relationship。此外，一些加合物已用于通过两步法制备对映体纯的4-烷基-5-甲酰基-4-硝基环己基-1-烯，涉及两步过程，即各自糖侧链的碱催化（NaOMe）脱乙酰化作用，以及随后的氧化裂解（NaIO 4）。当1a或1b与马来酸二甲酯，富马酸二甲酯或反式甲酯反应时用DBU（代替TMG）作为催化剂进行-4-氧戊烯酸酯，就地消除了亚硝酸。
• Enantioselective synthesis of cyclohexene nitroaldehydes
  作者：M.Ch. Moreno、J. Plumet、E. Román、J.A. Serrano、M.L. Rodríguez、C. Ruiz-Pérez

  DOI：10.1016/s0040-4039(00)99195-0

  日期：——
• MORENO, M. CH.;PLUMET, J.;ROMAN, E.;SERRANO, J. A.;RODRIGUEZ, M. L.;RUIZ-+, TETRAHEDRON LETT., 30,(1989) N4, C. 3179-3182
  作者：MORENO, M. CH.、PLUMET, J.、ROMAN, E.、SERRANO, J. A.、RODRIGUEZ, M. L.、RUIZ-+

  DOI：——

  日期：——