Allyl 2-acetamido-4,6-O-benzylidene-2-deoxy-α-D-allopyranoside | 136845-44-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: Allyl 2-acetamido-4,6-O-benzylidene-2-deoxy-α-D-allopyranoside
• 英文别名: N-[(2R,4aR,6S,7R,8S,8aS)-8-hydroxy-2-phenyl-6-prop-2-enoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-yl]acetamide
• CAS: 136845-44-8
• 化学式: C₁₈H₂₃NO₆
• 分子量: 349.384
• InChiKey: RZNDVHTWHYQMRO-PNVOZDDCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  86.2
• 氢给体数：
  2
• 氢受体数：
  6

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  ——	Allyl 2-acetamido-4,6-O-benzylidene-2-deoxy-3-O-(methanesulfonyl)-D-glucopyranoside	136773-78-9	C19H25NO8S	427.475
  ——	allyl 2-acetamido-2-deoxy-α,β-D-glucopyranoside	88903-97-3	C11H19NO6	261.275
  ——	D-GlcNAc	7512-17-6	C8H15NO6	221.21

• 下游产品

  中文名称	英文名称	CAS号	化学式	分子量
  ——	Allyl 2-acetamido-3-O-benzyl-4,6-O-benzylidene-2-deoxy-α-D-allopyranoside	137432-76-9	C25H29NO6	439.508
  ——	Allyl 6-O-benzyl-2-deoxy-2-phthalimido-α-D-allopyranoside	144221-84-1	C24H25NO7	439.465
  阿洛氨菌素	allosamidin	144539-85-5	C25H42N4O14	622.627

反应信息

• 作为反应物：
  描述：

  Allyl 2-acetamido-4,6-O-benzylidene-2-deoxy-α-D-allopyranoside 在 吡啶 、 sodium hydroxide 、 三乙胺 作用下， 以 甲醇 为溶剂， 反应 162.5h， 生成 Allyl 3-O-acetyl-4,6-O-benzylidene-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
• 作为产物：
  描述：

  Allyl 2-acetamido-4,6-O-benzylidene-2-deoxy-3-O-(methanesulfonyl)-D-glucopyranoside 在 水 、 sodium acetate 作用下， 以 various solvent(s) 为溶剂， 反应 40.0h， 以81%的产率得到Allyl 2-acetamido-4,6-O-benzylidene-2-deoxy-α-D-allopyranoside
  参考文献：
  名称：

  异蒜素的合成

  摘要：

  已经通过消旋异源别甲唑啉衍生物的区域选择性糖苷化与二糖三氯乙酰胺酸盐的收敛选择性方法，合成了异蒜胺素，一种新型的几丁质酶抑制剂。

  DOI：

  10.1039/c39910001099

文献信息

• Glycosylidene Carbenes. Part 4. Synthesis of Spirocyclopropanes from Acetamidoglycosylidene-Derived Diazirines
  作者：Andrea Vasella、Christian Witzig、Ren� Husi

  DOI：10.1002/hlca.19910740625

  日期：1991.9.18

  The synthesis of the first glycosylidene-derived 2-acetamido-2-deoxydiazirine 4 from N-acetylglucosamine 6 is described. Thus, 6 was transformed into the 3-O-mesylglucopyranoside 9 by glycosidation with allyl alcohol, benzylidenation, and mesylation (Scheme 2). Solvolysis of 9 gave the allopyranoside 10 which, upon benzylation and glycoside cleavage, yielded the hemiacetals 12. Using our established

  描述了由N-乙酰基葡糖胺6合成第一糖基亚烷基衍生的2-乙酰氨基-2-脱氧重氮嗪4。因此，通过用烯丙醇糖基化，亚苄基化和甲磺酰化，将6转化为3- O-甲磺酰基吡喃葡萄糖苷9（方案2）。9的溶剂分解产生了异氰基吡喃糖苷10，经苄基化和糖苷裂解后，生成了半缩醛12。使用我们建立的方法（通过内酯肟14和重氮丙啶16），12给了重氮4。在i-PrOH存在下将该二嗪嗪热解，得到二氢-1,3-恶唑5（反应路线1）；在丙烯腈存在下，获得了四个非对映异构体螺环丙烷17-20和对乙酰氨基苯甲醛21并通过制备进行了分离。HPLC（方案3）。17–20构型的分配基于NOE的测量结果以及CN基团的反磁各向异性的影响。与早先的结果一致的四个环丙烷的比例是合理的。
• Synthesis of allosamidin
  作者：Jean-Luc Maloisel、Andrea Vasella、Barry M. Trost、David L. van Vranken

  DOI：10.1039/c39910001099

  日期：——

  Allosamidin, a novel chitinase inhibitor has been synthesized by a convergent approach using a regioselective glycosidation of a racemic allosamizoline derivative, with a disaccharide trichloroacetamidate.

  已经通过消旋异源别甲唑啉衍生物的区域选择性糖苷化与二糖三氯乙酰胺酸盐的收敛选择性方法，合成了异蒜胺素，一种新型的几丁质酶抑制剂。
• 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).