methyl 3-C-allyl-4,6-O-benzylidene-3-deoxy-α-D-altropyranoside | 131529-45-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 3-C-allyl-4,6-O-benzylidene-3-deoxy-α-D-altropyranoside
• 英文别名: methyl 4,6-O-benzylidene-3-allyl-3-deoxy-α-D-altropyranoside；methyl 4,6-O-benzylidene-3-deoxy-3-(prop-2-enyl)-α-D-altropyranoside；methyl 4,6-O-benzylidene-3-deoxy-3-C-propenyl-α-D-glucopyranoside；methyl 4,6-O-benzylidene-3-deoxy-3-C-(prop-2-enyl)-α-D-altroside；(2R,4aR,6S,7S,8S,8aS)-6-methoxy-2-phenyl-8-prop-2-enyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-ol
• CAS: 131529-45-8
• 化学式: C₁₇H₂₂O₅
• 分子量: 306.359
• InChiKey: PPTRDACLCKKDAG-DBWAAGBOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 3-C-allyl-4,6-O-benzylidene-3-deoxy-α-D-altropyranoside 在 吡啶 、 2,6-二甲基吡啶 、 N-溴代丁二酰亚胺(NBS) 、 正丁基锂 、 硼烷四氢呋喃络合物 、 三氟化硼乙醚 、 四丁基氟化铵 、 sodium cyanoborohydride 、 barium carbonate 、 锌 作用下， 以 四氢呋喃 、 丙醇 、 四氯化碳 、 正己烷 、 二氯甲烷 、 水 为溶剂， 反应 96.5h， 生成 (3R,4R,5S)-3,5-bis[(tert-butyldimethylsilyl)oxy]-4-[3-{(tert-butyldimethylsilyl)oxy}propyl]oct-1-en-7-yne
  参考文献：
  名称：

  24,24-Dimethylvitamin D3-26,23-lactones and their 2α-functionalized analogues as highly potent VDR antagonists

  摘要：

  Novel vitamin D receptor (VDR) antagonists, 24,24-dimethyl-1alpha-hydroxyvitamin D-3-26,23-lactones (8 and 9) and their C2alpha functionalized analogues (8a-c and 9a-c) were efficiently synthesized and their biological activities were evaluated. The construction of vitamin D-3 triene skeleton was achieved by palladium-catalyzed alkenylative cyclization of A-ring precursor enyne (22 and 22a-c) with CD-ring bromoolefin having a 24,24-dimethyl-alpha-methylene-gamma-lactone unit on the side chain (13 and 14). The CD-ring precursors 13 and 14 were prepared by using chromium-mediated allylation of the aldehyde 10 derived from vitamin D-2. On the other hand, the A-ring enyne having 2alpha-(3-hydroxypropyl) group (22b) was newly synthesized from epoxide 15 using regio- and stereoselective alkylation methodology. The potency of the antagonistic activity of the newly designed analogues (8 and 9) increased up to 12 times that of TEI-9647 (2). Furthermore, introduction of the three motifs, that is, a methyl (8a and 9a), an omega-hydroxypropyl (8b and 9b) or an omega-hydroxypropoxyl group (8c and 9c) into the C2alpha position of 8 and 9, respectively, resulted in remarkable enhancement, up to 89 times, of the antagonistic activity on VDR. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.05.113
• 作为产物：
  描述：

  氯丙烯镁 、 methyl 2,3-anhydro-4,6-O-benzilidene-α-D-mannopyranoside 以 四氢呋喃 为溶剂， 以85%的产率得到methyl 3-C-allyl-4,6-O-benzylidene-3-deoxy-α-D-altropyranoside
  参考文献：
  名称：

  The synthesis and X-ray crystal structure of a cyclopentaannulated sugar; the first example of an intramolecular aldol cyclopentaannulation in carbohydrate chemistry

  摘要：

  在碱性条件下，1,4-二羰基化合物很容易发生环化反应，生成环戊二烯糖衍生物 6。

  DOI：

  10.1039/c39950001567

文献信息

• The Synthesis of Some Carbohydrate-Derived Precursors to Tylonolide, the Aglycon of the Antibiotic Tylosin
  作者：AB Hughes、RV Stick、DMG Tilbrook

  DOI：10.1071/ch9901681

  日期：——

  Treatment of methyl 2,3-anhydro-4,6-O-benzylidene-α-D-alloside with the anion derived from trimethyl(prop-1-ynyl)silane, allylmagnesium chloride or isobutenylmagnesium chloride introduces a three- or four- carbon substituent at C2 of the sugar. In each case, a hydroboration-oxidation sequence helps convert the centre of unsaturation in the new substituent into a carboxylic acid residue. Subsequent manipulations allow the introduction ofanother carbon at C6 of the sugar to give a highly functionalized precursor to the C1-C9 fragment of tylonolide, the aglycon of the antibiotic tylosin. Attempts at the introduction of an axial methyl group at C4 of the extended sugar also described.

  将 2,3-脱水-4,6-O-亚苄基-α-D-阿洛糖甲基与三甲基（丙-1-炔基）硅烷、烯丙基氯化镁或异丁烯基氯化镁衍生的阴离子进行处理，可在糖的 C2 处引入三碳或四碳取代基。在每种情况下，氢硼氧化顺序都有助于将新取代基中的不饱和中心转化为羧酸残基。随后的操作允许在糖的 C6 处引入另一个碳，从而得到高度官能化的前体，形成泰诺内酯的 C1-C9 片段，即抗生素泰罗菌素的苷元。此外，还介绍了在扩展糖的 C4 处引入轴向甲基的尝试。
• The synthesis and X-ray crystal structure of a cyclopentaannulated sugar; the first example of an intramolecular aldol cyclopentaannulation in carbohydrate chemistry
  作者：Andrew J. Wood、Paul R. Jenkins、John Fawcett、David R. Russell

  DOI：10.1039/c39950001567

  日期：——

  A 1,4-dicarbonyl compound 5 has been constructed by a sequence involving opening of a protected glucose epoxide with allyl magnesium chloride, alkylation and Wacker oxidation; the 1,4-dicarbonyl compound readily undergoes cyclisalion under basic conditions to produce a Cyclopentaannulated sugar derivative 6, whose structure was confirmed by X-ray crystallography.

  在碱性条件下，1,4-二羰基化合物很容易发生环化反应，生成环戊二烯糖衍生物 6。
• Honzawa, Shinobu; Yamamoto, Yasuhiro; Hirasaka, Koshiro, Heterocycles, 2003, vol. 61, p. 327 - 338
  作者：Honzawa, Shinobu、Yamamoto, Yasuhiro、Hirasaka, Koshiro、Takayama, Hiroaki、Kittaka, Atsushi

  DOI：——

  日期：——
• The Stereoselective Preparation of an Enantiomerically Pure Cyclopentane Using Intramolecular Aldol Cyclopentaannulation of a Glucose Derivative
  作者：Andrew J. Wood、David J. Holt、Maria-Consuelo Dominguez、Paul R. Jenkins

  DOI：10.1021/jo981225j

  日期：1998.11.1

  Methods for the annulation of carbohydrates have found extensive applications in organic synthesis. We report here a new protocol for the stereoselective conversion of glucose into an enantiomerically pure cyclopentane aldehyde 22. The readily available epoxide 15 was reacted with allyl Grignard to produce alcohol 16 in 86% yield. Swern oxidation followed by epimerization using triethylamine in N,N-dimethylformamide furnished the ketone 17 also in 86% yield. Regioselective deprotonation with lithium hexamethyldisilazane in THF was followed by methylation with methyl iodide and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidone as cosolvent to give 80% yield of ketone 18. Oxidation of ketone 18 by the Wacker procedure gave the 1,4-diketone 19 in 56% yield. Intramolecular aldol condensation occurred readily on treatment of diketone 19 with potassium tert-butoxide in toluene to furnish a 90% yield of enone 20. Treatment with N-bromosuccinimide produced the bromoester 21 in 72% yield, which was reduced to a mixture of aldehydes 22 (61%) and 23 (14%) with zinc shot in 2-propanol.
• Synthesis of new iso-C-nucleoside analogues from 2-(methyl 2-O-benzyl-4,6-O-benzylidene-3-deoxy-α-d-altropyranosid-3-yl)ethanal
  作者：Iran Otero、Holger Feist、Lidcay Herrera、Manfred Michalik、José Quincoces、Klaus Peseke

  DOI：10.1016/j.carres.2005.01.003

  日期：2005.3

  Treatment of 2-(methyl 2-O-benzyl-4,6-O-benzylidene-3-deoxy-alpha-D-altropyranosid-3-yl)ethanal with malononitrile, cyanoacetamide and 2-cyano-N-(4-methoxyphenyl)acetamide, respectively, in the presence of aluminium oxide yielded 2-cyano-4-(methyl 2-O-benzyl-4,6-O-benzylidene-3-deoxy-alpha-D-altropyranosid-3-yl)crotonic acid derivatives. Cyclization with sulfur and triethylamine was performed to synthesize the 2-amino-5-(methyl 2-O-benzyl-4,6-O-benzylidene-3-deoxy-alpha-D-altropyranosid-3-yl)thiophene-3-carbonic acid derivatives, which were treated with triethyl orthoformate/ammonia and triethyl orthoformate, respectively, to furnish 6-(methyl 2-O-benzyl-4,6-O-benzylidene-3-deoxy-alpha-D-altropyranosid-3-yl)thieno[2.3-d] pyrimidine derivatives. Deprotection in two steps afforded 2-amino-5-(1,6- anhydro-3-deoxy-beta-D-altropyranos-3-yl)thiophene-3-carbonitrile and 6-(1,6-anhydro-3-deoxy-beta-D-altropyranos-3-yl)thieno[2.3-d]pyrimidine derivatives, respectively. (c) 2005 Elsevier Ltd. All rights reserved.