(2R,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine | 872345-56-7

• 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,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine
• 英文别名: (2R,3S,4R,5R)-3,4-bis(benzyloxy)-2'-O-(tert-butyldiphenylsilyl)-2,5-bis(hydroxymethyl)pyrrolidine；DALDP；[(2R,3R,4S,5R)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-3,4-bis(phenylmethoxy)pyrrolidin-2-yl]methanol
• CAS: 872345-56-7
• 化学式: C₃₆H₄₃NO₄Si
• 分子量: 581.827
• InChiKey: ICEMFIVSMSWWRK-YSIHQZDESA-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,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以73%的产率得到(2R,3R,4S,5R)-3,4-dibenzyloxy-2,5-bis(hydroxymethyl)pyrrolidine
  参考文献：
  名称：

  Polyhydroxylated pyrrolidines, III. Synthesis of new protected 2,5-dideoxy-2,5-iminohexitols from d-fructose

  摘要：

  The readily available 3-O-benzoyl-4-O-benzyl-1,2-Oisopi-opylidene-beta-D-fructopyranose (6) was straightforwardly transformed into 5-azido-3-O-benzoyl-4-O-benzyl-5-deoxy-1,2-O-isopropylidene-beta-D-fructopyranose (8), after treatment under modified Garegg's conditions followed by reaction of the resulting 3-O-benzoyl-4-O-benzyl-5-deoxy-5-iodo-1,2-O-isopropylidene-alpha-L-sorbopyranose (7) with lithium azide in DMF O-debenzoylation at C(3) in 8, followed by oxidation and reduction caused the inversion of the configuration to afford the corresponding beta-D-psicopyranose derivative 11 that was transformed into the related 3,4-di-O-benzyl derivative 12. Cleavage of the acetonide of 12 to give 13 followed by O-tert-butyldiphenylsilylation afforded a resolvable mixture of 14 and 15. Compound 14 was transformed into (2R,3R,4S,5R)- (17) and (2R,3R,4S,5S)-3,4-dibenzyloxy-2',5'-di-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (18) either by a tandem Staudinger/intramolecular aza-Wittig process and reduction of the resulting intermediate 2 only into 18 by a high stereoselective catalytic hydrogenation. When 15 was subjected to the same protocol, (2S,3S,4R,5R)- (21) and (2R,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (22) were obtained, respectively. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.09.043
• 作为产物：
  描述：

  5-azido-3,4-di-O-benzyl-1-O-tert-butyldiphenylsilyl-5-deoxy-α-D-psicopyranose 在 镍 氢气 作用下， 以 甲醇 为溶剂， 反应 20.0h， 以62%的产率得到(2R,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine
  参考文献：
  名称：

  Polyhydroxylated pyrrolidines, III. Synthesis of new protected 2,5-dideoxy-2,5-iminohexitols from d-fructose

  摘要：

  The readily available 3-O-benzoyl-4-O-benzyl-1,2-Oisopi-opylidene-beta-D-fructopyranose (6) was straightforwardly transformed into 5-azido-3-O-benzoyl-4-O-benzyl-5-deoxy-1,2-O-isopropylidene-beta-D-fructopyranose (8), after treatment under modified Garegg's conditions followed by reaction of the resulting 3-O-benzoyl-4-O-benzyl-5-deoxy-5-iodo-1,2-O-isopropylidene-alpha-L-sorbopyranose (7) with lithium azide in DMF O-debenzoylation at C(3) in 8, followed by oxidation and reduction caused the inversion of the configuration to afford the corresponding beta-D-psicopyranose derivative 11 that was transformed into the related 3,4-di-O-benzyl derivative 12. Cleavage of the acetonide of 12 to give 13 followed by O-tert-butyldiphenylsilylation afforded a resolvable mixture of 14 and 15. Compound 14 was transformed into (2R,3R,4S,5R)- (17) and (2R,3R,4S,5S)-3,4-dibenzyloxy-2',5'-di-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (18) either by a tandem Staudinger/intramolecular aza-Wittig process and reduction of the resulting intermediate 2 only into 18 by a high stereoselective catalytic hydrogenation. When 15 was subjected to the same protocol, (2S,3S,4R,5R)- (21) and (2R,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (22) were obtained, respectively. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.09.043

文献信息

• Total synthesis of the 5-epimers of naturally occurring (−)-hyacinthacine A5 and unnatural (+)-hyacinthacine A4
  作者：Isidoro Izquierdo、María T. Plaza、Juan A. Tamayo、Fernando Sánchez-Cantalejo

  DOI：10.1016/j.tetasy.2007.09.014

  日期：2007.9

  (1R,2S,3R,5S,7aR)-1,2-Dihydroxy-3-hydroxymethyl-5-methylpyrrolizidine 10 [(+)-5-epihyacinthacine A5] and (1R,2S,3R,5S,7aS)-1,2-dihydroxy-3-hydroxymethyl-5-methylpyrrolizidine 17 [ent-5-epihyacinthacine A4] have been synthesized by either Horner–Wadsworth–Emmons (HWE) or Wittig methodology using aldehydes 6 and 13, prepared from (2R,3S,4R,5R)-3,4-dibenzyloxy-N-benzyloxycarbonyl-2′-O-tert-butyldiphenylsilyl-2

  （1 R，2 S，3 R，5 S，7a R）-1,2-二羟基-3-羟甲基-5-甲基吡咯烷核苷10 [（+）-5- Epi hyacinthacine A 5 ]和（1 R，2 S，3 R，5 S，7a S）-1,2-二羟基-3-羟甲基-5-甲基吡咯烷嗪17 [ ent --5- epi hyacinthacine A 4 ]由Horner-Wadsworth-Emmons（HWE）或Wittig合成使用方法的醛6和13，从（2制备ř，3小号，4 - [R，5 - [R）-3,4- dibenzyloxy- ñ -苄氧羰基-2' - ö -叔-butyldiphenylsilyl -2,5-双（羟甲基）吡咯烷5（部分保护DALDP）和（2 - [R ，3小号，4 - [R，5小号）-3,4- dibenzyloxy- ñ -苄氧羰基-2,5-双（羟甲基）-2' - Ô -pivaloylpyrrolidine
• A New Synthetic Approach to (+)-Hyacinthacine A₁and the First Total Synthesis and Absolute Configuration Assignment of Naturally Occurring (+)-Hyacinthacine A₆
  作者：Isidoro Izquierdo、María T. Plaza、Juan A. Tamayo、Fernando Sánchez-Cantalejo

  DOI：10.1002/ejoc.200700820

  日期：2007.12

  Naturally occurring (1S,2R,3R,7aR)-1,2-dihydroxy-3-hydroxymethylpyrrolizidine [(+)-hyacinthacine A1 (1)] and(1S,2R,3R,5R,7aR)-1,2-dihydroxy-3-hydroxymethyl-5-methylpyrrolizidine [(+)-hyacinthacine A6 (2)] have been synthesized by Wittig's methodology using aldehyde 7, prepared from (2R,3S,4R,5R)-3,4-bis(benzyloxy)-2′-O-(tert-butyldiphenylsilyl)-2,5-bis(hydroxymethyl)pyrrolidine (3, partially protected

  天然存在的 (1S,2R,3R,7aR)-1,2-dihydroxy-3-hydroxymethylpyrrolizidine [(+)-hyacinthacine A1 (1)] 和 (1S,2R,3R,5R,7aR)-1,2-dihydroxy -3-羟甲基-5-甲基吡咯里西啶 [(+)-hyacinthacine A6 (2)] 已通过 Wittig 的方法合成，使用醛 7，由 (2R,3S,4R,5R)-3,4-bis(benzyloxy)-制备2'-O-（叔丁基二苯基甲硅烷基）-2,5-双（羟甲基）吡咯烷（3，部分保护的 DALDP），作为同手性原料和适当的叶立德，得到相应的 α,β-不饱和酯 8 或酮9分别进行内酰胺化和还原胺化，得到相应的中间体pyrrolizidin-5-one 11和完全保护的吡咯里西啶14。化合物11和14分别很容易转化为上述风信子1和2。(© Wiley-VCH
• Total synthesis of natural (+)-hyacinthacine A6 and non-natural (+)-7a-epi-hyacinthacine A1 and (+)-5,7a-diepi-hyacinthacine A6
  作者：Isidoro Izquierdo、María T. Plaza、Juan A. Tamayo、Francisco Franco、Fernando Sánchez-Cantalejo

  DOI：10.1016/j.tet.2010.03.049

  日期：2010.5

  Naturally occurring (1S,2R,3R,5R,7aR)-1,2-dihydroxy-3-hydroxymethyl-5-methylpyrrolizidine [(+)-hyacinthacine A(6), 2] together with unnatural (1S,2R,3R,7aS)-1,2-dihydroxy-3-hydroxy-methylpyrrolizidine [(+)-7a-epi-hyacinthacine A(1), 3] and (1S,2R,3R,5S,7aS)-1,2-dihydroxy-3-hydroxy-methyl-5-methylpyrrolizidine [(+)-5,7a-diepi-hyacinthacine A(6), 4] have been synthesized from a DALDP derivative [5, (2R,35,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)-pyrrolidine], as the homochiral starting material. The synthetic process employed took advantages of Wittig methodology followed by internal lactamization, in the case of (+)-7a-epi-hyacinthacine A(1) (3), and reductive amination for (+)-hyacinthacine A(6) (2) and (+)-5,7a-diepi-hyacinthacine A(6) (4). (C) 2010 Elsevier Ltd. All rights reserved.
• Polyhydroxylated pyrrolidines, III. Synthesis of new protected 2,5-dideoxy-2,5-iminohexitols from d-fructose
  作者：Isidoro Izquierdo、María T. Plaza、Miguel Rodríguez、Francisco Franco、Alicia Martos

  DOI：10.1016/j.tet.2005.09.043

  日期：2005.12

  The readily available 3-O-benzoyl-4-O-benzyl-1,2-Oisopi-opylidene-beta-D-fructopyranose (6) was straightforwardly transformed into 5-azido-3-O-benzoyl-4-O-benzyl-5-deoxy-1,2-O-isopropylidene-beta-D-fructopyranose (8), after treatment under modified Garegg's conditions followed by reaction of the resulting 3-O-benzoyl-4-O-benzyl-5-deoxy-5-iodo-1,2-O-isopropylidene-alpha-L-sorbopyranose (7) with lithium azide in DMF O-debenzoylation at C(3) in 8, followed by oxidation and reduction caused the inversion of the configuration to afford the corresponding beta-D-psicopyranose derivative 11 that was transformed into the related 3,4-di-O-benzyl derivative 12. Cleavage of the acetonide of 12 to give 13 followed by O-tert-butyldiphenylsilylation afforded a resolvable mixture of 14 and 15. Compound 14 was transformed into (2R,3R,4S,5R)- (17) and (2R,3R,4S,5S)-3,4-dibenzyloxy-2',5'-di-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (18) either by a tandem Staudinger/intramolecular aza-Wittig process and reduction of the resulting intermediate 2 only into 18 by a high stereoselective catalytic hydrogenation. When 15 was subjected to the same protocol, (2S,3S,4R,5R)- (21) and (2R,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (22) were obtained, respectively. (c) 2005 Elsevier Ltd. All rights reserved.