Acetic acid (E)-(R)-8-(4-methoxy-benzyloxy)-3,7-dimethyl-oct-6-enyl ester | 149710-28-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: Acetic acid (E)-(R)-8-(4-methoxy-benzyloxy)-3,7-dimethyl-oct-6-enyl ester
• CAS: 149710-28-1
• 化学式: C₂₀H₃₀O₄
• 分子量: 334.456
• InChiKey: WPGKQIVZRNOHKS-XQDXXFRFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.53
• 重原子数：
  24.0
• 可旋转键数：
  11.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  44.76
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  Acetic acid (E)-(R)-8-(4-methoxy-benzyloxy)-3,7-dimethyl-oct-6-enyl ester 在 sodium hydroxide 作用下， 以 甲醇 、 水 为溶剂， 以94%的产率得到
  参考文献：
  名称：

  Studies directed toward the total synthesis of cerorubenic acid-III. 3. A convergent enantioselective approach involving new arrangements for the actuation of ring D cyclization

  摘要：

  A possible enantiocontrolled route to cerorubenic acid-III (1) is described herein. The central elements of the approach take advantage of the ready availability of both optical an of citronellol and of the tricyclic ketone 8. Although the absolute configuration of 1 is not known, its relative stereochemistry has been established by X-ray crystallography. On this basis, it is possible to match the reaction partners with the long-range view of establishing experimentally the actual configuration of 1. Assembly of the two structural halves was accomplished via a vinylstannane intermediate whose construction required utilization of an intramolecular S(N)2 displacement in order to overcome the weakly nucleophilic nature of a stannyl-substituted ester enolate. The coupling reaction leading to 38 and 39 proved highly stereoselective as before, thereby setting the stage for conversion to D-seco derivatives of 1 via anionic oxy-Cope rearrangement. Although this phase of the strategy had previously been worked out on simpler systems, 38, 39, and analogs therof isomerized with concomitant alpha-hydroxylation of the intermediate enolates. These conversions proceeded smoothly and efficiently. Although conditions were found that curtailed this adventitious oxygenation, the conversions proceeded so slowly that degradation was now competitive with the formation of 41 and 43.

  DOI：

  10.1021/jo00068a021
• 作为产物：
  描述：

  (R)-1-citronellyl acetate 在 叔丁基过氧化氢 、 selenium(IV) oxide 、 水杨酸 、 silver(l) oxide 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 46.0h， 生成 Acetic acid (E)-(R)-8-(4-methoxy-benzyloxy)-3,7-dimethyl-oct-6-enyl ester
  参考文献：
  名称：

  Studies directed toward the total synthesis of cerorubenic acid-III. 3. A convergent enantioselective approach involving new arrangements for the actuation of ring D cyclization

  摘要：

  A possible enantiocontrolled route to cerorubenic acid-III (1) is described herein. The central elements of the approach take advantage of the ready availability of both optical an of citronellol and of the tricyclic ketone 8. Although the absolute configuration of 1 is not known, its relative stereochemistry has been established by X-ray crystallography. On this basis, it is possible to match the reaction partners with the long-range view of establishing experimentally the actual configuration of 1. Assembly of the two structural halves was accomplished via a vinylstannane intermediate whose construction required utilization of an intramolecular S(N)2 displacement in order to overcome the weakly nucleophilic nature of a stannyl-substituted ester enolate. The coupling reaction leading to 38 and 39 proved highly stereoselective as before, thereby setting the stage for conversion to D-seco derivatives of 1 via anionic oxy-Cope rearrangement. Although this phase of the strategy had previously been worked out on simpler systems, 38, 39, and analogs therof isomerized with concomitant alpha-hydroxylation of the intermediate enolates. These conversions proceeded smoothly and efficiently. Although conditions were found that curtailed this adventitious oxygenation, the conversions proceeded so slowly that degradation was now competitive with the formation of 41 and 43.

  DOI：

  10.1021/jo00068a021