(2S,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine | 872345-55-6

• 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: (2S,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine
• 英文别名: [(2R,3R,4S,5S)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-3,4-bis(phenylmethoxy)pyrrolidin-2-yl]methanol
• CAS: 872345-55-6
• 化学式: C₃₆H₄₃NO₄Si
• 分子量: 581.827
• InChiKey: ICEMFIVSMSWWRK-AXXKPAGNSA-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：

  (2S,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine 在 4-二甲氨基吡啶 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 4 A molecular sieve 、 TEA 、 四丁基氟化铵 、 potassium carbonate 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 24.5h， 生成 (2R,3R,4S,5R)-2-Benzoyloxymethyl-3,4-bis-benzyloxy-5-formyl-pyrrolidine-1-carboxylic acid benzyl ester
  参考文献：
  名称：

  Polyhydroxylated pyrrolizidines. Part 8. Enantiospecific synthesis of looking-glass analogues of hyacinthacine A5 from DADP

  摘要：

  (1R,2S,3S,5R,7aR)-1,2-二羟基-3-羟甲基-5-甲基吡咯烷[(-)-3-表洋蓟碱A(5), 1a]和(1S,2R,3R,5S,7aS)-1,2-二羟基-3-羟甲基吡咯烷[(+)-3-表洋蓟碱A5, 1b]已通过Wittig法或霍纳-伍德沃德-埃蒙德法(HWE法)合成，分别使用醛4和醛9作为起始材料，这些醛均由(2S,3S,4R,5R)-3,4-二苄氧基-2'-O-叔丁基二苯基硅基-2,5-双(羟甲基)吡咯啶(2，部分保护的DADP)制得，以及适当的叶立德（ylides），随后通过α,β-不饱和酮5和10的还原胺化过程分别进行环化，最后进行完全去保护。© 2006 爱思唯尔有限公司。保留所有权利。

  DOI：

  10.1016/j.tet.2006.04.003
• 作为产物：
  描述：

  5-azido-3,4-di-O-benzyl-1-O-tert-butyldiphenylsilyl-5-deoxy-α-D-psicopyranose 在 sodium cyanoborohydride 、 溶剂黄146 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 生成 (2S,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

• Lipase-mediated synthesis of enantiomeric 2,5,6-trideoxy-2,5-iminohexitols
  作者：Isidoro Izquierdo、María T. Plaza、Juan A. Tamayo、Francisco Franco、Fernando Sánchez-Cantalejo

  DOI：10.1016/j.tet.2008.03.089

  日期：2008.5

  Syntheses of 2,5,6-trideoxy-2,5-imino-d-alditol (2, 6-deoxy-DADP) and its enantiomer (3) from tri-orthogonally protected derivatives of DADP have been developed employing lipase-mediated kinetic desymmetrization and protecting group manipulations. Thus, and as an example, the starting DADP derivative (4) was transformed into a new symmetrical 2,5-bis(hydroxymethyl)pyrrolidine (6) by sequential N-protection

  2,5,6-三脱氧-2,5-亚氨基d-糖醇（的合成2，6-脱氧DADP）及其对映体（3从DADP的三正交保护的衍生物）已经开发了采用脂肪酶介导的动力学非对称化和保护组操作。因此，并且作为实例，通过顺序的N-保护和双-O-去甲硅烷基化，将起始DADP衍生物（4）转化为新的对称的2,5-双（羟甲基）吡咯烷（6）。最好在乙酰化条件下进行脂肪酶介导的6脱对称，得到（2 R）-乙酰氧基甲基衍生物7。绝对配置和ee为7通过与同手性样品的化学相关性明确建立了它们。化合物7直接转化为目标2,5,6-三苯氧基-2,5-亚氨基己糖醇3。
• Polyhydroxylated pyrrolizidines. Part 8. Enantiospecific synthesis of looking-glass analogues of hyacinthacine A5 from DADP
  作者：Isidoro Izquierdo、María T. Plaza、Juan A. Tamayo、Miguel Rodríguez、Alicia Martos

  DOI：10.1016/j.tet.2006.04.003

  日期：2006.6

  (1R,2S,3S,5R,7aR)-1,2-Dihydroxy-3-hydroxymethyl-5-methylpyrrolizidine[(-)-3-epihyacinthacine A(5), 1a] and (1S,2R,3R,5S 7aS)-1,2-dihydroxy-3-hydroxymethylpyrrolizidine[(+)-3-epihyacinthacine A5, 1b] have been synthesized either by Wittig's or Horner-Wadsworth-Emmond's (HWE's) methodology using aldehydes 4 and 9, both prepared from (2S,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (2, partially protected DADP), and the appropriate ylides, followed by cyclization through an internal reductive amination process of the resulting alpha,beta-unsaturated ketones 5 and 10, respectively, and total deprotection. (c) 2006 Elsevier Ltd. All rights reserved.

  (1R,2S,3S,5R,7aR)-1,2-二羟基-3-羟甲基-5-甲基吡咯烷[(-)-3-表洋蓟碱A(5), 1a]和(1S,2R,3R,5S,7aS)-1,2-二羟基-3-羟甲基吡咯烷[(+)-3-表洋蓟碱A5, 1b]已通过Wittig法或霍纳-伍德沃德-埃蒙德法(HWE法)合成，分别使用醛4和醛9作为起始材料，这些醛均由(2S,3S,4R,5R)-3,4-二苄氧基-2'-O-叔丁基二苯基硅基-2,5-双(羟甲基)吡咯啶(2，部分保护的DADP)制得，以及适当的叶立德（ylides），随后通过α,β-不饱和酮5和10的还原胺化过程分别进行环化，最后进行完全去保护。© 2006 爱思唯尔有限公司。保留所有权利。
• 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.