3,4-O-isopropylidene-2-C-methyl-D-arabinono-1,5-lactone | 850359-46-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 3,4-O-isopropylidene-2-C-methyl-D-arabinono-1,5-lactone
• 英文别名: 3,4-O-isopropylidene-2-C-methyl-D-arabinonolactone；3,4-O-isopropylidene-2-C-methyI-D-arabinono-1,5-lactone；3,4-O-Isoprpylidene-D-arabinono-1,5-lactone；(3aR,7S,7aR)-7-hydroxy-2,2,7-trimethyl-4,7a-dihydro-3aH-[1,3]dioxolo[4,5-c]pyran-6-one
• CAS: 850359-46-5
• 化学式: C₉H₁₄O₅
• 分子量: 202.207
• InChiKey: LSSZLMQXDDXJDX-KCRUCZTKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3,4-O-isopropylidene-2-C-methyl-D-arabinono-1,5-lactone 在 三氟甲磺酸酐 、 sodium azide 作用下， 生成 (3aR,7R,7aS)-7-azido-2,2,7-trimethyl-4,7a-dihydro-3aH-[1,3]dioxolo[4,5-c]pyran-6-one
  参考文献：
  名称：

  4-C-Me-DAB 和 4-C-Me-LAB——对映体烷基支化吡咯烷亚氨基糖——是特异且有效的 α-葡萄糖苷酶抑制剂；丙酮作为唯一的保护基团

  摘要：

  的4-合成Ç -Me-DAB [1,4-二脱氧-1,4-亚氨基-4- Ç甲基d -arabinitol]从升-erythronolactone和4- Ç -Me-LAB [从d - erythronolactone] 只需要一个丙酮化物保护基团。讨论了 pH 值对 4 - C -Me-DAB的 NMR 谱[盐的p K a约为 8.4] 的影响，并说明了在分析偶联常数和化学位移时需要小心。4- C -Me-DAB（对于大鼠肠道蔗糖酶K i 0.89 μM，IC 50 0.41 μM）是一种有竞争力的——而 4- C-Me-LAB（用于大鼠肠道蔗糖酶K i 0.95 μM，IC 50 0.66 μM）是一种非竞争性的特异性和有效的 α-葡萄糖苷酶抑制剂。提供了 DAB、LAB、4 - C -Me-DAB、4 - C -Me-LAB 和 isoDAB（但不是 isoLAB）抑制 α-葡萄糖苷酶的基本原理。两者都是内质网

  DOI：

  10.1016/j.tetlet.2010.10.173
• 作为产物：
  描述：

  sodium cyanide 、 1-Deoxy-3,4-O-isopropylidene-D-erythro-2-pentulofuranose 生成 3,4-O-isopropylidene-2-C-methyl-D-arabinono-1,5-lactone
  参考文献：
  名称：

  Doubly carbon-branched pentoses: synthesis of both enantiomers of 2,4-di-C-methyl arabinose and 2-deoxy-2,4-di-C-methyl arabinose using only acetonide protection

  摘要：

  An acetonide is the only protecting group used in the synthesis of both the enantiomers of 2,4-di-C-methyl arabinose and 2-deoxy-2,4-di-C-methyl arabinose via the enantiomeric 3-C-methyl-L-erythronolactone [from 2-C-methyl-D-ribono-lactone or D-ribose] and 3-C-methyl-D-erythronolactone [from D-tagatose Or L-ribose]. NMR studies on unprotected C-methyl arabinoses show that methyl branching significantly affects the ratios of pyranose and furanose forms present in aqueous Solution. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2009.06.098

文献信息

• High yield protection of alcohols, including tertiary and base sensitive alcohols, as benzhydryl ethers by heating with diphenyldiazomethane in the absence of any other reagent
  作者：Daniel Best、Sarah F. Jenkinson、Sebastian D. Rule、Rosemary Higham、Thomas B. Mercer、Richard J. Newell、Alexander C. Weymouth-Wilson、George W.J. Fleet、Sigthor Petursson

  DOI：10.1016/j.tetlet.2008.02.042

  日期：2008.3

  can be introduced efficiently without the need for any acid or base catalysis and which is not prone to acid or base catalysed migration is a significant advantage for many syntheses. Benzhydryl [diphenylmethyl] ethers of sugar lactones are formed in high yield under neutral conditions when the corresponding alcohol is heated with diphenyldiazomethane in an inert solvent such as acetonitrile or toluene;

  对于许多合成而言，可在不需要任何酸或碱催化的情况下有效地引入保护基且不易于被酸或碱催化的迁移的保护基是重要的优点。当相应的醇与二苯基重氮甲烷在惰性溶剂（如乙腈或甲苯）中加热时，在中性条件下，糖内酯的苄基[二苯基甲基]醚可以高收率形成；这样就可以在没有任何其他试剂的情况下轻松保护对碱敏感的和高度受阻的叔醇。
• Hydroxylated C-branched pyrrolidines, C-branched prolines and C-branched piperidines from a 2-C-methyl sugar lactone; efficient azide displacement of a tertiary triflate with inversion of configuration
  作者：Filipa P. da Cruz、Graeme Horne、George W.J. Fleet

  DOI：10.1016/j.tetlet.2008.09.069

  日期：2008.11

  The versatility of 3,4-O-isopropylidene-2-C-methyl-d-arabinonolactone [from d-erythronolactone] as a chiron for complex piperidines and pyrrolidines is illustrated by the synthesis of (2R,3S,4S)- and (2R,3S,4R)-dihydroxy-2-C-methyl prolines, 1,4-dideoxy-1,4-imino-4-C-methyl-l-ribitol and 1,4-dideoxy-1,4-imino-4-C-methyl-l-arabinitol, and isofagomine derivatives; the enantiomeric series is equally accessible

  3,4-的通用性Ô异亚丙基-2- Ç甲基- d-arabinonolactone [从d-erythronolactone]作为Chiron公司复杂哌啶和吡咯烷是通过合成出（2R，3S，4S） -和（ 2R，3S，4R）-二羟基-2- C-甲基脯氨酸，1,4-二脱氧-1,4-亚氨基-4- C-甲基-1-核糖醇和1,4-二脱氧-1,4-亚氨基-脯氨酸4 - C -1-甲基-1-阿拉伯糖醇和异黄酮衍生物；对映体系列同样可从1-赤藓内酯获得。
• Amadori ketoses with calcium hydroxide and the Kiliani reaction on 1-deoxy ketoses: two approaches to the synthesis of saccharinic acids
  作者：David J. Hotchkiss、Sarah F. Jenkinson、Richard Storer、Thomas Heinz、George W.J. Fleet

  DOI：10.1016/j.tetlet.2005.11.018

  日期：2006.1

  aldonic acids) may be formed by treatment of Amadori ketoses with calcium hydroxide or by the Kiliani reaction of 1-deoxy ketoses with cyanide. Thus (i) N,N-dibenzyl or N,N-dimethyl-1-amino-1-deoxy-d-fructose with aqueous calcium hydroxide afforded 2-C-methyl-d-ribono-1,4-lactone under green conditions and (ii) reaction of methyl magnesium bromide with 2,3-O-isopropylidene-d-erythronolactone gave 1-deoxy-3

  可以通过用氢氧化钙处理Amadori酮糖或通过1-脱氧酮糖与氰化物的Kiliani反应来形成糖精酸（2- C-甲基醛糖酸）。因此，（i）N，N-二苄基或N，N-二甲基-1-氨基-1-脱氧-d-果糖与氢氧化钙水溶液在绿色条件下得到2 - C-甲基-d-核糖-1,4-内酯。 （ii）使甲基溴化镁与2，3 - O-异亚丙基-d-异乙内酯反应，得到1-脱氧-3，4- O-异亚丙基-d-核糖，随后用氰化钠水溶液处理并水解， 2 C-甲基-d-阿拉伯糖基-1,4-内酯。这样的支链糖内酯可能具有作为含有支链碳链的Chirons的价值。
• Anomeric stereospecific synthesis of 2′-C-methyl β-nucleosides; the Holy reaction of cyanamide with 2-C-methyl-d-arabinose
  作者：Sarah F. Jenkinson、Nigel A. Jones、Adel Moussa、Alistair J. Stewart、Thomas Heinz、George W.J. Fleet

  DOI：10.1016/j.tetlet.2007.04.105

  日期：2007.6

  of 2-C-methyl-d-arabinose with cyanamide and methyl propiolate afford an anhydronucleoside, which may be opened under acid conditions with inversion at C2′, to give 2′-C-methyl uridine; ring opening with sodium hydroxide gave 2′-C-methyl arabino-uridine with retention of configuration at C2′. This gives complete stereospecific control to yield only β-nucleosides.

  2 - C-甲基-d-阿拉伯糖与氰酰胺和丙酸甲酯的顺序反应提供了脱水核苷，其可以在酸性条件下打开并在C2'处转化，得到2'- C-甲基尿苷；用氢氧化钠开环得到2'- C-甲基阿拉伯糖-尿苷，其在C2'处的构型得以保留。这提供了完全的立体定向控制，仅产生β-核苷。
• WO2007/75876
  申请人：——

  公开号：——

  公开（公告）日：——