(2R,3R,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine | 487040-55-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3R,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine
• 英文别名: [(2R,3R,4R,5R)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-3,4-bis(phenylmethoxy)pyrrolidin-2-yl]methanol
• CAS: 487040-55-1
• 化学式: C₃₆H₄₃NO₄Si
• 分子量: 581.827
• InChiKey: ICEMFIVSMSWWRK-BAQBVXSRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.07
• 重原子数：
  42
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  60
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,3R,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine 在 palladium on activated charcoal N-甲基吗啉 、 四氧化锇 、 四丙基高钌酸铵 、 氢气 、 sodium methylate 、 potassium carbonate 、 O-(4-氯苯甲酰)氢奎宁 、 N-甲基吗啉氧化物 作用下， 以 甲醇 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 105.0h， 生成 (1S,2R,5R,6R,7R,7aR)-6,7-dibenzyloxy-5-tert-butyldiphenylsilyloxymethyl-1,2-dihydroxypyrrolizidin-3-one
  参考文献：
  名称：

  Polyhydroxylated pyrrolizidines. Part 6: A new and concise stereoselective synthesis of (+)-casuarine and its 6,7-diepi isomer, from DMDP

  摘要：

  A new synthesis for (+)-casuarine (1) and its 6,7-diepi isomer (15) in a stereocontrolled manner, is reported herein. All appropriately protected polyhydroxylated pyrrolidine, such as (2R,3R,4R,5R)-3,4-dibenzyloxy-2'-O-tet-t-butyldiphenylsilyl-2,5-bis(hydroxymethl)pyrrolidine (3, protected DMDP), easily available from D-fructose, was chosen as the chiral starting material. Compounds 1 and 15 were obtained from 3, in seven steps, in a 23.2 and 20.5% overall yields, respectively. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.05.004
• 作为产物：
  描述：

  5-azido-3,4-di-O-benzyl-5-deoxy-β-D-fructopyranose 在 镍 咪唑 、 氢气 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 20.0 ℃ 、344.74 kPa 条件下， 反应 36.0h， 生成 (2R,3R,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine
  参考文献：
  名称：

  Polyhydroxylated pyrrolidines. Part II: Highly stereoselective synthesis of partially protected DMDP derivatives from d-fructose

  摘要：

  The readily available 3,4-di-O-benzyl-1,2-O-isopropylidene-beta-D-fructopyranose 2 was straightforwardly transformed into 5-azido-3,4-di-O-benzyl-5-deoxy-1,2-O-isopropylidene-beta-D-fructopyranose 4, after treatment under modified Garegg's conditions followed by reaction of the resulting 3,4-di-O-benzyl-5-deoxy-5-iodo-1,2-O-isopropylidene-alpha-L-sorbopyranose 3 with sodium azide in DMF. Cleavage of the acetonide of 4 to afford 6 followed by regioselective O-tert-butyldiphenylsilylation at C(1)OH afforded 7. Hydrogenation of 7 proceeded with high stereoselectivity yielding 3,4-di-O-benzyl-1-O-tert-butyldiphenylsilyl-2,5-dideoxy-2,5-imino-D-mannitol 1, confirmed by its O-desilylation to 8. Compound 1 was subjected to different N-protection reactions to afford the corresponding N-allyl (1a), N-benzyl (1b), and N-tert-butyloxycarbonyl (1c) derivatives. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00369-5

文献信息

• Polyhydroxylated pyrrolizidines. Part 6: A new and concise stereoselective synthesis of (+)-casuarine and its 6,7-diepi isomer, from DMDP
  作者：Isidoro Izquierdo、María T. Plaza、Juan A. Tamayo

  DOI：10.1016/j.tet.2005.05.004

  日期：2005.7

  A new synthesis for (+)-casuarine (1) and its 6,7-diepi isomer (15) in a stereocontrolled manner, is reported herein. All appropriately protected polyhydroxylated pyrrolidine, such as (2R,3R,4R,5R)-3,4-dibenzyloxy-2'-O-tet-t-butyldiphenylsilyl-2,5-bis(hydroxymethl)pyrrolidine (3, protected DMDP), easily available from D-fructose, was chosen as the chiral starting material. Compounds 1 and 15 were obtained from 3, in seven steps, in a 23.2 and 20.5% overall yields, respectively. (c) 2005 Elsevier Ltd. All rights reserved.
• Polyhydroxylated pyrrolidines. Part II: Highly stereoselective synthesis of partially protected DMDP derivatives from d-fructose
  作者：Isidoro Izquierdo、Marı́a T. Plaza、Francisco Franco

  DOI：10.1016/s0957-4166(02)00369-5

  日期：2002.8

  The readily available 3,4-di-O-benzyl-1,2-O-isopropylidene-beta-D-fructopyranose 2 was straightforwardly transformed into 5-azido-3,4-di-O-benzyl-5-deoxy-1,2-O-isopropylidene-beta-D-fructopyranose 4, after treatment under modified Garegg's conditions followed by reaction of the resulting 3,4-di-O-benzyl-5-deoxy-5-iodo-1,2-O-isopropylidene-alpha-L-sorbopyranose 3 with sodium azide in DMF. Cleavage of the acetonide of 4 to afford 6 followed by regioselective O-tert-butyldiphenylsilylation at C(1)OH afforded 7. Hydrogenation of 7 proceeded with high stereoselectivity yielding 3,4-di-O-benzyl-1-O-tert-butyldiphenylsilyl-2,5-dideoxy-2,5-imino-D-mannitol 1, confirmed by its O-desilylation to 8. Compound 1 was subjected to different N-protection reactions to afford the corresponding N-allyl (1a), N-benzyl (1b), and N-tert-butyloxycarbonyl (1c) derivatives. (C) 2002 Elsevier Science Ltd. All rights reserved.