(S)-2-[(4R,5S,6S)-2,2-Di-tert-butyl-6-((S)-1-[1,3]dithiolan-2-yl-ethyl)-5-methyl-[1,3,2]dioxasilinan-4-yl]-thiopropionic acid S-benzyl ester | 193416-17-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-2-[(4R,5S,6S)-2,2-Di-tert-butyl-6-((S)-1-[1,3]dithiolan-2-yl-ethyl)-5-methyl-[1,3,2]dioxasilinan-4-yl]-thiopropionic acid S-benzyl ester
• 英文别名: S-benzyl (2S)-2-[(4R,5S,6S)-2,2-ditert-butyl-6-[(1S)-1-(1,3-dithiolan-2-yl)ethyl]-5-methyl-1,3,2-dioxasilinan-4-yl]propanethioate
• CAS: 193416-17-0
• 化学式: C₂₇H₄₄O₃S₃Si
• 分子量: 540.928
• InChiKey: ROHPBWWKYXELCX-JQZONJITSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.99
• 重原子数：
  34
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  111
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (S)-2-[(4R,5S,6S)-2,2-Di-tert-butyl-6-((S)-1-[1,3]dithiolan-2-yl-ethyl)-5-methyl-[1,3,2]dioxasilinan-4-yl]-thiopropionic acid S-benzyl ester 在 mercury(II) perchlorate 、 iron(III)-acetylacetonate 、 phosphate buffer pH 7.4 、 戴斯-马丁氧化剂 、 氟化氢吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 6.41h， 生成 denticulatin A
  参考文献：
  名称：

  Enantioselective total synthesis of (−)-denticulatins A and B using a novel group-selective aldolization of a meso dialdehyde as a key step

  摘要：

  The diastereoselective synthesis of (-)-denticulatin A (1a) was achieved for the first time in 9 steps (41% yield) based on a novel group-selective aldolization of a meso dialdehyde as a key step. The inherent chirality present in bornanesultam 4 was thus transmitted to the five stereocenters spanning C-4-C-8 in key intermediate 8. In addition, denticulatin B (1b) was obtained from the common intermediate 8 en route to denticulatin A in 10 steps and 35% overall yield. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00617-0
• 作为产物：
  描述：

  (3S,4S,5S,6R)-4-(tert-Butyl-dimethyl-silanyloxy)-6-[(S)-2-((1R,5S,7S)-10,10-dimethyl-3,3-dioxo-3λ⁶-thia-4-aza-tricyclo[5.2.1.0^1,5]dec-4-yl)-1-methyl-2-oxo-ethyl]-3,5-dimethyl-tetrahydro-pyran-2-one 在 2,6-二甲基吡啶 、 二异丁基氢化铝 、 zinc(II) iodide 作用下， 以 二氯甲烷 为溶剂， 反应 15.0h， 生成 (S)-2-[(4R,5S,6S)-2,2-Di-tert-butyl-6-((S)-1-[1,3]dithiolan-2-yl-ethyl)-5-methyl-[1,3,2]dioxasilinan-4-yl]-thiopropionic acid S-benzyl ester
  参考文献：
  名称：

  Enantioselective total synthesis of (−)-denticulatins A and B using a novel group-selective aldolization of a meso dialdehyde as a key step

  摘要：

  The diastereoselective synthesis of (-)-denticulatin A (1a) was achieved for the first time in 9 steps (41% yield) based on a novel group-selective aldolization of a meso dialdehyde as a key step. The inherent chirality present in bornanesultam 4 was thus transmitted to the five stereocenters spanning C-4-C-8 in key intermediate 8. In addition, denticulatin B (1b) was obtained from the common intermediate 8 en route to denticulatin A in 10 steps and 35% overall yield. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00617-0

文献信息

• Non-destructive Removal of the Bornanesultam Auxiliary in ?-SubstitutedN-Acylbornane-10,2-sultanis under Mild Conditions: An efficient synthesis of enantiomerically pure ketones and aldehydes
  作者：Wolfgang Oppolzer、Christophe Darcel、Patrick Rochet、Stephane Rosset、Jef De Brabander

  DOI：10.1002/hlca.19970800502

  日期：1997.8.11

  two-step procedure involving a known mercaptolysis reaction followed by an [Fe(acac)3]-mediated coupling of the resulting S-benzyl thioesters with Grignard reagents. Furthermore, enantiomerically pure aldehydes 23 can be obtained from α-substituted N-acylbornane-10,2-sultams 6via a one-step reduction with (i-Bu)2AIH. No epimerization at the α-chiral center is observed during the cleavage reaction whereby

  α-替补Ñ -acylbornane-10，2 -sultams 6,9，和10可以被转换成纯对映异构体酮5. 13，和14，分别经由涉及已知mercaptolysis反应，随后通过的[Fe两步过程（acac）3 ]-介导的所得S-苄基硫酯与格氏试剂的偶联。此外，对映体纯的醛23可以通过（i-Bu）2的一步还原从α-取代的N-酰基冰片烷-10,2-杜鹃花6获得。AIH。在切割反应过程中未观察到在α-手性中心的差向异构体，由此回收了手性助剂，硼烷-10，2-sultam 1或ent - 1。通过使用这种方法，可以制备几种天然产物或其前体。
• Enantioselective total synthesis of (−)-denticulatins A and B using a novel group-selective aldolization of a meso dialdehyde as a key step
  作者：Jef De Brabander、Wolfgang Oppolzer

  DOI：10.1016/s0040-4020(97)00617-0

  日期：1997.7

  The diastereoselective synthesis of (-)-denticulatin A (1a) was achieved for the first time in 9 steps (41% yield) based on a novel group-selective aldolization of a meso dialdehyde as a key step. The inherent chirality present in bornanesultam 4 was thus transmitted to the five stereocenters spanning C-4-C-8 in key intermediate 8. In addition, denticulatin B (1b) was obtained from the common intermediate 8 en route to denticulatin A in 10 steps and 35% overall yield. (C) 1997 Elsevier Science Ltd.