Allyl 6-O-benzyl-2-deoxy-2-phthalimido-α-D-allopyranoside | 144221-84-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Allyl 6-O-benzyl-2-deoxy-2-phthalimido-α-D-allopyranoside
• 英文别名: 2-[(2S,3R,4S,5S,6R)-4,5-dihydroxy-6-(phenylmethoxymethyl)-2-prop-2-enoxyoxan-3-yl]isoindole-1,3-dione
• CAS: 144221-84-1
• 化学式: C₂₄H₂₅NO₇
• 分子量: 439.465
• InChiKey: LHOJYEPFFIHXDW-DVMSJWTNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  32
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  106
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (5R,6R,7S,8R)-6,7,8-三(苄氧基)-5-[(苄氧基)甲基]-4-氧杂-1,2-二氮杂螺[2.5]辛-1-烯 、 Allyl 6-O-benzyl-2-deoxy-2-phthalimido-α-D-allopyranoside 以 1,4-二氧六环 为溶剂， 反应 4.0h， 以72%的产率得到allyl 6-O-benzyl-2-deoxy-2-phthalimido-3-O-(2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-α-D-allopyranoside
  参考文献：
  名称：

  亚糖基卡宾。第19部分。烯丙基2-脱氧-2-邻苯二甲酰亚胺基-D-吡喃果糖苷的区域选择性糖基化

  摘要：

  已经研究了部分重保护的单醇3和7，二醇2和8以及三醇4被重氮1的糖基化的区域选择性和立体选择性。α-D-二醇2的糖基化（方案2）选择性地产生1,3-连接的二糖11和12（80％，α-D/β-D9：1），而与βD-异头物的类似反应8导致异头连接的1,3-和1,4-二糖13（12.5％），14（16％），15（13％）和16的混合物（20.5％；表2）。卡宾分子的O H –C（4）为2的质子化通过以下观察证明：α-D-单醇3在其他条件相同的情况下不与1反应，并且β-D-醇7主要产生的βd葡萄糖苷18（52％）之外的14％17。类似地，作为二醇的苷化2，的氢键的影响ħ OC（4）上的卡宾的接近方向，作用ħ三元醇4与1的反应证明了OC（4）在卡宾的质子化中的立体电子控制以及在确保确保氧碳阳离子的拦截中的立体电子控制（方案3），主要导致了α-D构型的1,3-除了其端基异构体20（16％）和一些4-取

  DOI：

  10.1002/hlca.19940770724
• 作为产物：
  描述：

  Allyl 4,6-O-benzylidene-2-deoxy-2-phthalimido-α-D-allopyranoside 在 盐酸 、 乙醚 、 4 A molecular sieve 、 sodium cyanoborohydride 作用下， 生成 Allyl 6-O-benzyl-2-deoxy-2-phthalimido-α-D-allopyranoside
  参考文献：
  名称：

  Synthesis ofN-Acetylallosamine-Derived Disaccharides

  摘要：

  AbstractThe protected disaccharide 44, a precursor for the synthesis of allosamidin, was prepared from the glycosyl acceptor 8 and the donors 26–28, best yields being obtained with the trichloroacetimidate 28 (Scheme 6). Glycosidation of 8 or of 32 by the triacetylated, less reactive donors 38–40 gave the disaccharides 46 and 45, respectively, in lower yields (Scheme 7). Regioselective glycosidation of the diol 35 by the donors 38–40 gave 42, the axial, intramolecularly H‐bonded OHC(3) group reacting exclusively (Scheme 5). The glycosyl acceptor 8 was prepared from 9 by reductive opening of the dioxolane ring (Scheme 3). The donors 26–28 were prepared from the same precursor 9 via the hemiacetal 25. To obtain 9, the known 10 was de‐N‐acetylated (→ 18), treated with phthalic anhydride (→ 19), and benzylated, leading to 9 and 23 (Schemes 2 and 3). Saponification of 23, followed by acetylation also gave 9. Depending upon the conditions, acetylation of 19 yielded a mixture of 20 and 21 or exclusively 20. Deacetylation of 20 led to the hydroxyphthalamide 22. De‐N‐acetylation of the 3‐O‐benzylated β‐D‐glycosides 11 and 15, which were both obtained from 10, was very sluggish and accompanied by partial reduction of the O‐allyl to an O‐propyl group (Scheme 2). The β‐D‐glycoside 30 behaved very similarly to 11 and 15. Reductive ring opening of 31, derived from 29, yielded the 3‐O‐acetylated acceptor 32, while the analogous reaction of the β‐D‐anomer 20 was accompanied by a rapid 3‐O→4‐O acyl migration (→34; Scheme 4). Reductive ring opening of 21 gave the diol 35. The triacetylated donors 38–40 were obtained from 20 by debenzylidenation, acetylation (→36), and deallylation (→37), followed by either acetylation (→38), treatment with Me3SiSEt (→39), or Cl3CCN (→ 40).

  DOI：

  10.1002/hlca.19920750505

文献信息

• Glycosylidene Carbenes. Part 19. Regioselective glycosidation of allyl 2-deoxy-2-phthalimido-D-allopyranosides
  作者：Karin Briner、Bruno Bernet、Jean-Luc Maloisel、Andrea Vasella

  DOI：10.1002/hlca.19940770724

  日期：1994.11.2

  Protonation of the carbene by OH–C(4) of 2 is evidenced by the observation that the α-D-mono-alcohol 3 did not react with 1 under otherwise identical conditions, and that the β-D-alcohol 7 yielded predominantly the β-D-glucoside 18 (52%) besides 14% of 17. Similarly as for the glycosidation of the diol 2, the influence of the H-bond of HOC(4) on the direction of approach of the carbene, the role of HOC(4)

  已经研究了部分重保护的单醇3和7，二醇2和8以及三醇4被重氮1的糖基化的区域选择性和立体选择性。α-D-二醇2的糖基化（方案2）选择性地产生1,3-连接的二糖11和12（80％，α-D/β-D9：1），而与βD-异头物的类似反应8导致异头连接的1,3-和1,4-二糖13（12.5％），14（16％），15（13％）和16的混合物（20.5％；表2）。卡宾分子的O H –C（4）为2的质子化通过以下观察证明：α-D-单醇3在其他条件相同的情况下不与1反应，并且β-D-醇7主要产生的βd葡萄糖苷18（52％）之外的14％17。类似地，作为二醇的苷化2，的氢键的影响ħ OC（4）上的卡宾的接近方向，作用ħ三元醇4与1的反应证明了OC（4）在卡宾的质子化中的立体电子控制以及在确保确保氧碳阳离子的拦截中的立体电子控制（方案3），主要导致了α-D构型的1,3-除了其端基异构体20（16％）和一些4-取
• Synthesis ofN-Acetylallosamine-Derived Disaccharides
  作者：Jean-Luc Maloisel、Andrea Vasella

  DOI：10.1002/hlca.19920750505

  日期：1992.8.13

  AbstractThe protected disaccharide 44, a precursor for the synthesis of allosamidin, was prepared from the glycosyl acceptor 8 and the donors 26–28, best yields being obtained with the trichloroacetimidate 28 (Scheme 6). Glycosidation of 8 or of 32 by the triacetylated, less reactive donors 38–40 gave the disaccharides 46 and 45, respectively, in lower yields (Scheme 7). Regioselective glycosidation of the diol 35 by the donors 38–40 gave 42, the axial, intramolecularly H‐bonded OHC(3) group reacting exclusively (Scheme 5). The glycosyl acceptor 8 was prepared from 9 by reductive opening of the dioxolane ring (Scheme 3). The donors 26–28 were prepared from the same precursor 9 via the hemiacetal 25. To obtain 9, the known 10 was de‐N‐acetylated (→ 18), treated with phthalic anhydride (→ 19), and benzylated, leading to 9 and 23 (Schemes 2 and 3). Saponification of 23, followed by acetylation also gave 9. Depending upon the conditions, acetylation of 19 yielded a mixture of 20 and 21 or exclusively 20. Deacetylation of 20 led to the hydroxyphthalamide 22. De‐N‐acetylation of the 3‐O‐benzylated β‐D‐glycosides 11 and 15, which were both obtained from 10, was very sluggish and accompanied by partial reduction of the O‐allyl to an O‐propyl group (Scheme 2). The β‐D‐glycoside 30 behaved very similarly to 11 and 15. Reductive ring opening of 31, derived from 29, yielded the 3‐O‐acetylated acceptor 32, while the analogous reaction of the β‐D‐anomer 20 was accompanied by a rapid 3‐O→4‐O acyl migration (→34; Scheme 4). Reductive ring opening of 21 gave the diol 35. The triacetylated donors 38–40 were obtained from 20 by debenzylidenation, acetylation (→36), and deallylation (→37), followed by either acetylation (→38), treatment with Me3SiSEt (→39), or Cl3CCN (→ 40).