(4R,5R,Z)-4-ethynyl-5-propenyl-2,2,4-trimethyl-1,3-dioxolane | 202814-82-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4R,5R,Z)-4-ethynyl-5-propenyl-2,2,4-trimethyl-1,3-dioxolane
• CAS: 202814-82-2
• 化学式: C₁₁H₁₆O₂
• 分子量: 180.247
• InChiKey: LDSGMNBGESIVAQ-RSWVCDQLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.11
• 重原子数：
  13.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (4R,5R,Z)-4-ethynyl-5-propenyl-2,2,4-trimethyl-1,3-dioxolane 在 manganese(IV) oxide 、 cerium(III) chloride 、 lithium hexamethyldisilazane 作用下， 以 二氯甲烷 为溶剂， 反应 3.5h， 生成 1-[1-(tert-Butyl-dimethyl-silanyloxy)-anthracen-2-yl]-3-[(4R,5R)-2,2,4-trimethyl-5-((Z)-propenyl)-[1,3]dioxolan-4-yl]-propynone
  参考文献：
  名称：

  Highly Selective DNA Alkylation at the 5‘ Side G of a 5‘GG3‘ Sequence by an Aglycon Model of Pluramycin Antibiotics through Preferential Intercalation into the GG Step

  摘要：

  Altromycin B and kapurimycin Ag are new members of the pluramycin family antibiotics that alkylate N7 of guanine (G) in duplex DNA at an epoxide subunit attached to the C2 position of the pyranone ring. While 5'AG3' selective alkylation by altromycin B was accounted for by selective binding to the sequence, it remained uncertain why kapurimycin A(3), which is structurally similar to an aglycon part of altromycin B but has an epoxide subunit with an opposite absolute configuration, selectively alkylates 5' G of the 5'GG3' sequence. To clarify the molecular basis for the sequence-selective G alkylation by kapurimycin A(3), we have examined the DNA cleavage sequence selectivity of an enantiomeric pair of an aglycon model of pluramycin antibiotics and calculated total energy change upon intercalation of the model into a specific sequence by means of the DFT-HF hybrid method at the B3LYP/6-31G(d) level. Only an enantiomer with the same epoxide absolute configuration as that of kapurimycin Ag showed a remarkable G alkylation reactivity with a high selectivity for 5' G of the 5'GG3' sequence, Molecular mechanics calculations suggested that the intercalation of the aglycon model in an orientation perpendicular to neighboring base pairs is essential for the effective G alkylation at 5' G of GN sequences, and the efficiency for G alkylation is not dependent upon the sequence being intercalated. DFT-HF hybrid calculations suggested that the intercalation of the model is energetically most favorable into GG step. These results suggested that highly 5' G selective alkylation of the GG sequence by kapurimycin A(3) arises from a selective intercalation into the GG step. Stacking interaction with both 5' and 3' side Gs is a basis for the stabilization of the intercalated complex.

  DOI：

  10.1021/ja980801q
• 作为产物：
  描述：

  (E)-1-[(4-methoxyphenyl)methoxy]-3-methylpent-2-en-4-yne 在 甲醇 、 甲基磺酰胺 、 AD-mix-β 、 camphor-10-sulfonic acid 、 sodium methylate 、 双(三甲基硅烷基)氨基钾 、 戴斯-马丁氧化剂 、 copper(II) sulfate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 lithium hexamethyldisilazane 作用下， 以 二氯甲烷 、 水 、 丙酮 、 叔丁醇 为溶剂， 反应 64.5h， 生成 (4R,5R,Z)-4-ethynyl-5-propenyl-2,2,4-trimethyl-1,3-dioxolane
  参考文献：
  名称：

  Highly Selective DNA Alkylation at the 5‘ Side G of a 5‘GG3‘ Sequence by an Aglycon Model of Pluramycin Antibiotics through Preferential Intercalation into the GG Step

  摘要：

  Altromycin B and kapurimycin Ag are new members of the pluramycin family antibiotics that alkylate N7 of guanine (G) in duplex DNA at an epoxide subunit attached to the C2 position of the pyranone ring. While 5'AG3' selective alkylation by altromycin B was accounted for by selective binding to the sequence, it remained uncertain why kapurimycin A(3), which is structurally similar to an aglycon part of altromycin B but has an epoxide subunit with an opposite absolute configuration, selectively alkylates 5' G of the 5'GG3' sequence. To clarify the molecular basis for the sequence-selective G alkylation by kapurimycin A(3), we have examined the DNA cleavage sequence selectivity of an enantiomeric pair of an aglycon model of pluramycin antibiotics and calculated total energy change upon intercalation of the model into a specific sequence by means of the DFT-HF hybrid method at the B3LYP/6-31G(d) level. Only an enantiomer with the same epoxide absolute configuration as that of kapurimycin Ag showed a remarkable G alkylation reactivity with a high selectivity for 5' G of the 5'GG3' sequence, Molecular mechanics calculations suggested that the intercalation of the aglycon model in an orientation perpendicular to neighboring base pairs is essential for the effective G alkylation at 5' G of GN sequences, and the efficiency for G alkylation is not dependent upon the sequence being intercalated. DFT-HF hybrid calculations suggested that the intercalation of the model is energetically most favorable into GG step. These results suggested that highly 5' G selective alkylation of the GG sequence by kapurimycin A(3) arises from a selective intercalation into the GG step. Stacking interaction with both 5' and 3' side Gs is a basis for the stabilization of the intercalated complex.

  DOI：

  10.1021/ja980801q

文献信息

• Highly Selective DNA Alkylation at the 5‘ Side G of a 5‘GG3‘ Sequence by an Aglycon Model of Pluramycin Antibiotics through Preferential Intercalation into the GG Step
  作者：Kazuhiko Nakatani、Akimitsu Okamoto、Takahiro Matsuno、Isao Saito

  DOI：10.1021/ja980801q

  日期：1998.11.1

  Altromycin B and kapurimycin Ag are new members of the pluramycin family antibiotics that alkylate N7 of guanine (G) in duplex DNA at an epoxide subunit attached to the C2 position of the pyranone ring. While 5'AG3' selective alkylation by altromycin B was accounted for by selective binding to the sequence, it remained uncertain why kapurimycin A(3), which is structurally similar to an aglycon part of altromycin B but has an epoxide subunit with an opposite absolute configuration, selectively alkylates 5' G of the 5'GG3' sequence. To clarify the molecular basis for the sequence-selective G alkylation by kapurimycin A(3), we have examined the DNA cleavage sequence selectivity of an enantiomeric pair of an aglycon model of pluramycin antibiotics and calculated total energy change upon intercalation of the model into a specific sequence by means of the DFT-HF hybrid method at the B3LYP/6-31G(d) level. Only an enantiomer with the same epoxide absolute configuration as that of kapurimycin Ag showed a remarkable G alkylation reactivity with a high selectivity for 5' G of the 5'GG3' sequence, Molecular mechanics calculations suggested that the intercalation of the aglycon model in an orientation perpendicular to neighboring base pairs is essential for the effective G alkylation at 5' G of GN sequences, and the efficiency for G alkylation is not dependent upon the sequence being intercalated. DFT-HF hybrid calculations suggested that the intercalation of the model is energetically most favorable into GG step. These results suggested that highly 5' G selective alkylation of the GG sequence by kapurimycin A(3) arises from a selective intercalation into the GG step. Stacking interaction with both 5' and 3' side Gs is a basis for the stabilization of the intercalated complex.