(4S,5R,6S)-4-<(1R,3R,4S,5R,7R)-8-(tert-Butyldimethylsilyloxy)-4-hydroxy-1,3,5,7-tetramethyloctyl>-6-ethyl-2,2,5-trimethyl-1,3-dioxane | 129117-22-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4S,5R,6S)-4-<(1R,3R,4S,5R,7R)-8-(tert-Butyldimethylsilyloxy)-4-hydroxy-1,3,5,7-tetramethyloctyl>-6-ethyl-2,2,5-trimethyl-1,3-dioxane
• 英文别名: (2R,4R,5S,6R,8R)-1-[tert-butyl(dimethyl)silyl]oxy-8-[(4S,5R,6S)-6-ethyl-2,2,5-trimethyl-1,3-dioxan-4-yl]-2,4,6-trimethylnonan-5-ol
• CAS: 129117-22-2
• 化学式: C₂₇H₅₆O₄Si
• 分子量: 472.825
• InChiKey: QHKSPPIAOSMGBX-XSGVOWHTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.26
• 重原子数：
  32
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4S,5R,6S)-4-<(1R,3R,4S,5R,7R)-8-(tert-Butyldimethylsilyloxy)-4-hydroxy-1,3,5,7-tetramethyloctyl>-6-ethyl-2,2,5-trimethyl-1,3-dioxane 在 吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 重铬酸吡啶 、 tris(triphenylphosphine)ruthenium(II) chloride 、 cerium(III) chloride 、 18-冠醚-6 、 Zeolite 3A 、 2,4,6-三氯苯甲酰氯 、 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 potassium carbonate 、 三乙胺 作用下， 反应 3.0h， 生成 Acetic acid (9E,15E)-(1R,5S,6R,8R,11R,17R)-5-((1R,3R,4S,5S)-4-hydroxy-1,3,5-trimethyl-6-oxo-octyl)-1-methoxy-6,8,16,18-tetramethyl-3-oxo-4,21-dioxa-bicyclo[15.3.1]henicosa-9,15,18-trien-11-yl ester
  参考文献：
  名称：

  文丘里汀A和B-II糖苷的全合成。

  摘要：

  合成了文丘里汀A和B糖苷配基3的C 15 -C 27片段2，然后通过2的酯与先前合成的C 1 -C 14片段1的分子内WittigHomer反应完成3的全合成。

  DOI：

  10.1016/s0040-4039(00)88867-x
• 作为产物：
  描述：

  (2S,3S)-3-<(tertbutyl)dimethylsilyloxy>-2-methylpentanal 在 咪唑 、 2-羟基吡啶 、 lithium aluminium tetrahydride 、 四丁基氟化铵 、 potassium carbonate 作用下， 以 甲醇 、 乙醚 为溶剂， 生成 (4S,5R,6S)-4-<(1R,3R,4S,5R,7R)-8-(tert-Butyldimethylsilyloxy)-4-hydroxy-1,3,5,7-tetramethyloctyl>-6-ethyl-2,2,5-trimethyl-1,3-dioxane
  参考文献：
  名称：

  Synthesis of a C-15/C-27 segment of venturicidine

  摘要：

  The C-15/C-27 segment of venturicidine contains a 1,3,5,n-anti-methylated alkyl chain, which resembles syndiotactic polypropylene and should therefore favor an extended conformation. A synthetic scheme is presented, by which such structures are generated in a cycle of four steps per three stereogenic centers. This allowed the synthesis of the above mentioned venturicidine fragment in 15 steps from propionaldehyde.

  DOI：

  10.1016/s0040-4039(00)76958-9

文献信息

• Synthesis of the C15–C27 portion of venturicidins: a formal total synthesis of venturicidin X
  作者：Keiji Tsunashima、Mitsuaki Ide、Hiroshi Kadoi、Aya Hirayama、Masaya Nakata

  DOI：10.1016/s0040-4039(01)00518-4

  日期：2001.5

  The C15–C27 portion of venturicidin X was prepared using substitution reactions of alkyl trifluoromethanesulfonates with a vinylmetal compound followed by homogeneous hydrogenation. Together with our previous synthesis of the C1–C14 portion of venturicidin X, a formal total synthesis of venturicidin X was completed.

  使用三氟甲磺酸烷基酯与乙烯基金属化合物的取代反应，然后进行均相氢化，制备文丘里丁X的C15–C27部分。连同我们先前合成的文丘里丁X的C1-C14部分，完成了文丘里丁X的正式全合成。
• Stereoselective Synthesis of Alcohols, L. Stereoselective Synthesis of a C-15/C-27 Segment of the Venturicidines
  作者：Reinhard W. Hoffmann、Ulrike Rolle、Richard Göttlich

  DOI：10.1002/jlac.199619961104

  日期：1996.11

  Chain extension of an aldehyde by two “propionate” units has been attained by stereoselective allylboration with the chiral 1-methylbutenyl boronate 3 to give, e.g., the homoallylic alcohol 6, followed by a regioselective hydroboration/carbonylation procedure to give, e.g., the epimeric aldehydes 8. The latter were converted into the lactols 10, which equilibrated to the desired epimer. The lactols

  通过与手性的1-甲基丁烯基硼酸酯3进行立体选择性的烯丙基硼化得到例如均丙醇6，然后进行区域选择性的硼氢化/羰基化过程得到例如的差向异构体，可以使醛通过两个“丙酸酯”单元进行链扩展。醛8。后者被转化为内酯10，其平衡为所需的差向异构体。内酯可以再次进行烯丙基硼化反应，引发第二轮扩链方案。该技术已被用于以15个步骤合成文丘二烯C-15 / C-27片段23，该片段包含8个具有适当绝对构型的立体异构中心。
• Synthesis of C15–C27 segment of venturicidine X by utilizing desymmetrization protocol
  作者：J.S. Yadav、Sk. Samad Hossain、Debendra K. Mohapatra

  DOI：10.1016/j.tetlet.2010.05.148

  日期：2010.8

  We have achieved the synthesis of C15-C27 fragment of venturicidine X using desymmetrization protocol, substrate-controlled Grignard reaction, Barton-McCombie reaction, Sharpless epoxidation, and TBSOTf-mediated rearrangement to produce the aldol product through a non-aldol route as the key step following 23 longest linear sequences with 6.4% overall yield starting from a known intermediate 11. (C) 2010 Elsevier Ltd. All rights reserved.
• AKITA, HIROYUKI;YAMADA, HARUTAMI;MATSUKURA, HIROKO;NAKATA, TADASHI;OISHI,+, TETRAHEDRON LETT., 31,(1990) N2, C. 1735-1738
  作者：AKITA, HIROYUKI、YAMADA, HARUTAMI、MATSUKURA, HIROKO、NAKATA, TADASHI、OISHI,+

  DOI：——

  日期：——
• Synthesis of a C-15/C-27 segment of venturicidine
  作者：Reinhard W. Hoffmann、Ulrike Rolle

  DOI：10.1016/s0040-4039(00)76958-9

  日期：1994.7

  The C-15/C-27 segment of venturicidine contains a 1,3,5,n-anti-methylated alkyl chain, which resembles syndiotactic polypropylene and should therefore favor an extended conformation. A synthetic scheme is presented, by which such structures are generated in a cycle of four steps per three stereogenic centers. This allowed the synthesis of the above mentioned venturicidine fragment in 15 steps from propionaldehyde.