(-)-(1S,4R,5R,6R)-5-exo-(benzeneselenyl)-6-endo-chloro-3-methylidene-7-oxabicyclo<2.2.1>heptan-2-one | 134160-51-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (-)-(1S,4R,5R,6R)-5-exo-(benzeneselenyl)-6-endo-chloro-3-methylidene-7-oxabicyclo<2.2.1>heptan-2-one
• 英文别名: (1S,4R,5R,6R)-6-endo-chloro-3-methylidene-5-benzeneselenyl-7-oxabicyclo<2.2.1>heptan-2-one；(-)-(1S,4R,5R,6R)-6-endo-chloro-3-methylidene-5-exo-(phenylseleno)-7-oxabicyclo[2.2.1]heptan-2-one；5-exo-benzeneselenyl-6-endo-chloro-3-methylidene-7-oxabicyclo[2.2.1]heptan-2-one；(1S,4R,5R,6R)-6-endo-chloro-3-methylidene-5-benzeneselenyl-7-oxabicyclo[2.2.1]heptan-2-one；(1S,4R,5R,6R)-6-chloro-3-methylidene-5-phenylselanyl-7-oxabicyclo[2.2.1]heptan-2-one
• CAS: 134160-51-3
• 化学式: C₁₃H₁₁ClO₂Se
• 分子量: 313.642
• InChiKey: FICVYQAZJBJIJE-JHEVNIALSA-N

物化性质

• 沸点：
  459.9±45.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.32
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (-)-(1S,4R,5R,6R)-5-exo-(benzeneselenyl)-6-endo-chloro-3-methylidene-7-oxabicyclo<2.2.1>heptan-2-one 在 吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 sodium azide 、 偶氮二异丁腈 、 三苯基氢化锡 、 三溴化硼 、 间氯过氧苯甲酸 、 3-氯苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 8.58h， 生成 (+)-(1R,2S,5S,6R)-5-azido-3-chloro-2-hydroxy-6-(1',3',4',5'-tetra-O-acetyl-2',6'-anhydro-7'-deoxy-D-glycero-D-manno-heptitol-7'-C-yl)cyclohex-3-en-7-yl acetate
  参考文献：
  名称：

  The C-Disaccharide α-C(1→3)-Mannopyranoside of N-Acetylgalactosamine Is an Inhibitor of Glycohydrolases and of Human α-1,3-Fucosyltransferase VI. Its Epimer α-(1→3)-Mannopyranoside of N-Acetyltalosamine Is Not

  摘要：

  The radical C-glycosidation of (-)-(1S,4R,5R,6R)-6-endo-chloro-3-methylidene-5-exo-(phenylseleno)-7-oxabicyclo[2.2.1]heptan-2-one ((-)-4) with 2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl bromide gave (+)-(1S,3R,4R,5R,6R)-6-endo-chloro-5-exo-(phenylseleno)-3-endo-(1',3',4',5'-tetra-O-acetyl-2',6'-anhydro-7'-deoxy-D-glycero-D-manno-heptitol-7'-C-yl)-7-oxabicyclo[2.2.1]hept-2-one ((+)-5) that was converted into (+)-(1R,2S,5R,6R)-5-acetamido-3-chloro-2-anhydro-6-(1R,2S,5R,6R)-5-acetamido-3-chloro-2-hydroxy-6-(1',3',4',5'-tetra-O-acetyl)-2',6'-anhydro-7'-deoxy-D- glycero-D-manno-heptitol-7'-C-yl)cyclohex-3-en-1-yl acetate ((+)-10) and into (+)-(1R,2S,5R,6S)-5-bromo-3-chloro-2-hydroxy-6-(1',3',4',5',-tetra-O-acetyl-2',6'-anhydro-7'-deoxy-D-glycero-D-manno-heptitol-7'-C-yl)cyclohex-3-en-1-yl acetate ((+)-19). Ozonolysis of (+)-10 and further transformations provided 2-acetamido-2,3-dideoxy-3-C-(2',6'-anhydro-7'-deoxy-D-glycero-D-manno- heptitol-7'-C-yl)-D-galactose (alpha-C(1-->3)-D-mannopyranoside of N-acetylgalactosamine (alpha-D-Manp-(1-->3)CH2-D-GalNAc): 1). Displacement of the bromide (+)-19 with NaN3 in DMF provided the corresponding azide ((-)-20) following a SN2 mechanism. Ozonolysis of (-)-20 and further transformations led to 2-acetamido-2,3-dideoxy-3-C-(2',6'-anhydro-7'-deoxy-D-glycerol-D-manno-heptitol-7'-C-yl)-D-talose (alpha-C(1-->3)-D-mannopyranoside of N-acetyl D-talosamine (alpha-D-Manp-(1-->3)CH2-D-TalNAc): 2). The neutral C-disaccharide 1 inhibits several glycosidases (e.g., beta-galactosidase from jack bean with K-i = 7.5 mu M, alpha-L-fucosidase from human placenta with K-i = 28 mu M, beta-glucosidase from Caldocellum saccharolyticum with K-i = 18 mu M) and human alpha-1,3-fucosyltransferase VI (Fuc-TVI) with K-i = 120 mu M whereas it 2-epimer 2 does not. Double reciprocal analysis showed that the inhibition of Fuc-TVI by 1 displays a mixed pattern with respect to both the donor sugar GDP-fucose and the acceptor LacNAc with K-i of 123 and 128 mu M, respectively.

  DOI：

  10.1021/jo991952u
• 作为产物：
  描述：

  n,n-二甲基亚甲基碘化胺 、 (-)-(1S,4R,5R,6R)-5-exo-benzeneselenyl-2-<(tert-butyl)dimethylsilyloxy>-6-endo-chloro-7-oxabicyclo<2.2.1>hept-2-ene 在 六甲基磷酰三胺 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以84%的产率得到(-)-(1S,4R,5R,6R)-5-exo-(benzeneselenyl)-6-endo-chloro-3-methylidene-7-oxabicyclo<2.2.1>heptan-2-one
  参考文献：
  名称：

  Synthesis of α-(1→3)- and α-(1→4)-linked c-disaccharides using (+)-7-oxabicyclo[2.2.1]hept-5-en-2-one (“naked sugar”).

  摘要：

  DOI：

  10.1016/0040-4039(91)80349-b

文献信息

• Enantiomerically pure 7-oxabicyclo[2.2.1]hept-5-en-2-yl derivatives (naked sugars) as synthetic intermediates. 18. Synthesis of .alpha.-(1.fwdarw.2)-, .alpha.-(1.fwdarw.3)-, .alpha.-(1.fwdarw.4)-, and .alpha.-(1.fwdarw.5)-C-linked disaccharides through 2,3,4,6-tetra-O-acetylglucopyranosyl radical additions to 3-methylidene-7-oxabicyclo[2.2.1]heptan-2-one derivatives
  作者：R. Mampuya Bimwala、Pierre Vogel

  DOI：10.1021/jo00033a032

  日期：1992.3

  The ''naked sugar'' (+)-1 (1R,2S,4R)-2-cyano-7-oxabicyclo[2.2.1]hept-5-en-2-yl (1S')-camphanate) has been converted into (+)-(1R,4R,5R,6R)-3-methylidene-5-exo,6-exo(isopropylidenedioxy)-7-oxabicyclo[2.2.1]heptan-2-one ((+)-3) and (-)-(1S,4R,5R,6R)-5-exo-(benzeneselenyl)-6-endo-chloro-3-methylidene-7-oxabicyclo[2.2.1]heptan-2-one ((-)-26). Reductive addition of 2,3,4,6-tetra-O-acetylglucopyranosyl radical onto (+)-3 and (-)-26 were highly stereoselective giving exclusively 3-endo-(glucosylmethyl)-7-oxabicyclo[2.2.1]heptan-2-one derivatives. The anomeric selectivity (alpha-C-glucoside vs beta-C-glucoside) was 5.5:1 with (+)-3 and 8:1 with (-)-26. The C-glucosides so-obtained were transformed into alpha-(1 --> 2)-, alpha-(1 --> 3)-, alpha-(1 --> 4)-, and alpha-(1 --> 5)-C-linked disaccharide derivatives which combine alpha-D-glucopyranose with L-altro-hexonolactone, L-manno-hexonolactone, L-mannose, and L-(talo-hexofuranosid)uronic acid, respectively.
• Synthesis of α-C(1→3)-mannopyranoside of N-acetylgalactosamine, a new β-galactosidase inhibitor
  作者：Carla Pasquarello、Raynald Demange、Pierre Vogel

  DOI：10.1016/s0960-894x(99)00064-5

  日期：1999.3

  Radical C-glycosidation of a 3-methylidene-7-oxabicyclo[2.2.1]heptan-2-one derivative with acetobromomannose gave a alpha-C-mannopyranoside that was converted into alpha-D-ManpCH(2)(1-->3)-D-GalNAc, a C-disaccharide that inhibits beta-galactosidase from jack bean with IC50 = 9.4 mu M and K-i = 7.5 mu M (mixed mode of inhibition). (C) 1999 Elsevier Science Ltd. All rights reserved.
• SYNTHESIS OF THE C-DISACCHARIDE α-C(1→3)-L-FUCOPYRANOSIDE OF N-ACETYLGALACTOSAMINE1
  作者：Cécile Viodé2、Pierre Vogel

  DOI：10.1081/car-100108286

  日期：——

  Radical C-glycosidation of racemic 5-exo-benzeneselenyl-6-endo-chloro-3-methylidene-7-oxabicyclo[2.2.1]heptan-2-one ((+/-)-2) with alpha -acetobromofucose (3) provided a mixture of alpha -C-fucosides that were reduced with NaBH4 to give two diastereomeric alcohols that were separated readily. One of them ((-)-6) was converted into (-)-methyl 2-acetamido-4-O-acetyl-2,3-dideoxy-3-C(3',4',5'-tri-O-acetyl-2',6'-anhydro- 1',7'-dideoxy-alpha -L-glycero-D-galacto-heptitol-1'-C-yl)-alpha -D-galactopyranuronate ((-)-11) and then into (-)-methyl 2-acetamido-2,3-dideoxy-3-C-(2',6'-anhydro- 1',7'-dideoxy-alpha -L-glycero-D-galacto-heptitol- 1'-C-yl)-beta -D-galactopyranoside a new alpha -C(1 -->3)-L-fucopyranoside of N-acetylgalactosamine. Its H-1 NMR data shows that this C-disaccharide (alpha -L-Fucp-(1 -->3)CH2-beta -D-GaINAc-OMe) adopts a major conformation in solution similar to that expected for the corresponding O-linked disaccharide, i.e., with antiperiplanar sigma (C-3',C-2') and sigma (C-1',C-3) bonds.
• Synthesis of α-D-(1→3) and α-D-(1→4)-C-linked galactosides of D-mannose derivatives. Conformation of α-C-galactosides.
  作者：Rafael Ferritto、Pierre Vogel

  DOI：10.1016/s0957-4166(00)86285-0

  日期：1994.11

  Reductive radical alpha-D-galactosidation of 5-exo-(benzeneselenyl)-6-endo-chloro-3-methylidene-7- -oxabicyclo[2.2.1]heptan-2-one with acetobromo-D-galactose, followed by ketone reduction led to (+)-(1R,2S, 3R,4S,5S,6S)-5-exo-(benzeneselenyl)-6-endo-chloro-3-endo-[(2',3',4',6'-tetra-O-acetyl-alpha-D-galactopyranosyl)me- thyl]-7-oxabicyclo[2.2.1]heptan-2-endo-ol which was converted into (+)-methyl 3-deoxy-3-[(alpha-D-galactopyranosyl)methyl]-alpha-D-mannopyranoside (1), (+)-3-deoxy-3-[alpha-D-galactopyranosyl)methyl]-D-mannitol (2) and 4-deoxy-4-[(2',3',4',6'-tetra-O-acetyl-alpha-D-galactopyranosyl)methyl]-2,3,6-tri-O-acetyl-D-mannono-1,5-lactone (3). H-1-MNR data of the alpha-C-galactosides confirmed that their preferred conformations involve antiperiplanar arrangements for the C-linked substrates and bond sigma C(1'),C(2') of the alpha-(1-->3)-C-galactoside unit. The alpha-(1-->3)-C-galactoside of methyl mannopyranoside 1 adopts a conformation similar to that proposed for methyl 3-O-(alpha-D-galactopyranosyl)-alpha-D-mannopyranoside.