2,3:6,7-Di-O-isopropyliden-D-glycero-D-guloheptonono-γ-lacton | 14548-95-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3:6,7-Di-O-isopropyliden-D-glycero-D-guloheptonono-γ-lacton
• 英文别名: (3aR,6S,6aR)-6-[(R)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-hydroxymethyl]-2,2-dimethyl-6,6a-dihydro-3aH-furo[3,4-d][1,3]dioxol-4-one
• CAS: 14548-95-9
• 化学式: C₁₃H₂₀O₇
• 分子量: 288.298
• InChiKey: ZAVQWRAEZCFXGE-HOTMZDKISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  83.4
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2,3:6,7-Di-O-isopropyliden-D-glycero-D-guloheptonono-γ-lacton 在 吡啶 、 叠氮化锂 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 生成 (-)-5-azido-5-deoxy-2,3:6,7-di-O-isopropylidene-D-glycero-L-manno-heptono-1,4-lactone
  参考文献：
  名称：

  （+）-3,7,8-三甲氧基-3,7-亚氨基-d-苏--1-半乳糖辛醇的合成及其对β-葡萄糖苷酶的抑制作用

  摘要：

  易于获得的2,3：6,7-二-O-异亚丙基-D-甘油-D-古洛庚酮-1,4-内酯[（-）-5]通过四个合成步骤转化为新的亚氨基辛醇（ +）-3,7,8-三甲氧基-3,7-亚氨基-D-苏-L-半乳糖辛醇[（+）-10]。尽管（+）-10的哌啶单元具有β-D-半乳糖-己吡喃糖苷的绝对构型，但该亚氨基糖醇不会抑制5种市售的β-半乳糖苷酶。但是，发现（+）-10是来自杏仁（Ki = 15μM）和来自解糖Caldocellum saccharolyticum（Ki = 41μM）的β-葡萄糖苷酶的良好竞争性抑制剂。

  DOI：

  10.1016/0008-6215(95)00348-7
• 作为产物：
  描述：

  葡庚糖酸内酯 在 对甲苯磺酸 作用下， 以 丙酮 为溶剂， 反应 21.0h， 生成 2,3:6,7-Di-O-isopropyliden-D-glycero-D-guloheptonono-γ-lacton
  参考文献：
  名称：

  （+）-3,7,8-三甲氧基-3,7-亚氨基-d-苏--1-半乳糖辛醇的合成及其对β-葡萄糖苷酶的抑制作用

  摘要：

  易于获得的2,3：6,7-二-O-异亚丙基-D-甘油-D-古洛庚酮-1,4-内酯[（-）-5]通过四个合成步骤转化为新的亚氨基辛醇（ +）-3,7,8-三甲氧基-3,7-亚氨基-D-苏-L-半乳糖辛醇[（+）-10]。尽管（+）-10的哌啶单元具有β-D-半乳糖-己吡喃糖苷的绝对构型，但该亚氨基糖醇不会抑制5种市售的β-半乳糖苷酶。但是，发现（+）-10是来自杏仁（Ki = 15μM）和来自解糖Caldocellum saccharolyticum（Ki = 41μM）的β-葡萄糖苷酶的良好竞争性抑制剂。

  DOI：

  10.1016/0008-6215(95)00348-7

文献信息

• Efficient conditions for the synthesis of C-glycosylidene derivatives: a direct and stereoselective route to C-glycosyl compounds
  作者：Y Lakhrissi、C Taillefumier、M Lakhrissi、Y Chapleur

  DOI：10.1016/s0957-4166(99)00586-8

  日期：2000.2

  Efficient conditions for the synthesis of C-glycosylidene compounds from lactones based on Wittig reactions of cyanomethyl triphenylphosphoranylidene involving microwave heating are described: subsequent stereoselective reduction of the anomeric olefins gave the corresponding C-glycosides in good yields with high stereocontrol.

  描述了基于氰基甲基三苯基磷杂亚烷基的涉及微波加热的Wittig反应从内酯合成C-糖基亚基化合物的有效条件：随后的异头烯烃的立体选择性还原以良好的收率和高的立体控制得到了相应的C-糖苷。
• An Expedient Synthesis of LAF389, a Bengamide B Analogue
  作者：David D. Xu、Liladhar Waykole、John V. Calienni、Lech Ciszewski、George T. Lee、Wenming Liu、Joanna Szewczyk、Kevin Vargas、Kapa Prasad、Oljan Repič、Thomas J. Blacklock

  DOI：10.1021/op0341162

  日期：2003.11.1

  convergent, safe synthesis of LAF389 (9), an anti-cancer agent analogous to bengamide B, is described. Starting from α-d-glucoheptonic (d-glycero-d-gulo-heptonic acid) γ-lactone (10), the lactone 15 was constructed in five steps. Major improvements were made in the preparation of the aldehyde precursor 14 and subsequent olefination to yield 15 via a modified Julia protocol. This olefination was significantly

  描述了 LAF389 (9) 的优化、收敛、安全合成，这是一种类似于苯甲酰胺 B 的抗癌剂。从α-d-葡庚糖（d-甘油-d-古洛庚酸）γ-内酯（10）开始，分五步构建内酯15。在醛前体 14 的制备和随后的烯烃化以通过改进的 Julia 方案产生 15 方面进行了重大改进。通过使用 TMSCl 作为添加剂，这种烯烃化得到了显着改善。药物物质的第二个片段，ε-己内酰胺 7，是从 (5R)-5-羟基-l-赖氨酸 (1) 中通过两次一锅法获得的。最后，使用 2-乙基己酸钠 (Na-EH) 用 7 打开 15，得到 8，其脱保护得到 LAF389。
• Synthesis of β-D-(1→3)-C-linked 1,5,6-trideoxy-1,5-iminogalactoside of D-altrose derivatives
  作者：Alain Baudat、Pierre Vogel

  DOI：10.1016/0040-4039(95)02214-7

  日期：1996.1

  The title aza-C-disaccharides were obtained through a highly stereoselective cross-aldolisation of a 2,6,7-trideoxy-2,6-imino-D-glycero-L-mannose and a 7-oxanorbornanone derivative.

  标题氮杂-C-二糖是通过2,6,7-三苯氧基-2,6-亚氨基-D-甘油-L-甘露糖和7-氧杂草烷酮衍生物的高度立体选择性交叉醛缩醛化获得的。
• Stereoselective syntheses of 2,4:5,6-di-O-isopropylidene-1 -C-phenyl-<scp>D</scp>-glycero-<scp>D</scp>-ido-hexitol and 2,4:5,6-di-O-isopropylidene-1 -C-phenyl-<scp>D</scp>-glycero-<scp>D</scp>-gulo-hexitol from<scp>D</scp>-glycero-<scp>D</scp>-gulo-heptono-γ-lactone. X-Ray structure of 1 -O-acetyl-2,4:5,6-di-O-isopropylidene-1-C-phenyl-<scp>D</scp>-glycero-<scp>D</scp>-ido-hexitol
  作者：Tony K. M. Shing、Hon-Chung Tsui、Zhao-Hui Zhou、Thomas C. W. Mak

  DOI：10.1039/p19920000887

  日期：——

  D-glycero-D-gulo-Heptonolactone has been converted by three consecutive reactions (acetonation, reduction and glycol cleavage reaction) into 2,4:5,6-di-O-isopropylidene-D-glucose which with phenylmagnesium bromide gave preponderantly 2,4:5,6-di-O-isopropylidene-1-C-phenyl-D-glycero-D-ido-hexitol 5. 2,4:5,6-Di-O-isopropylidene-1-C-phenyl-D-glycero-D-gulo-hexitol 6 has been obtained from 5 via an oxidation-reduction sequence. The structure of 5 has been confirmed by X-ray crystallographic analysis of its 1-O-acetyl-derivative 12.
• Aza-<i>C</i>-disaccharides:  Synthesis of 6-Deoxygalactonojirimycin β-C(1→3) Linked with <scp>d</scp>-Altrofuranosides and <scp>d</scp>-Galactose
  作者：Alain Baudat、Pierre Vogel

  DOI：10.1021/jo970151t

  日期：1997.9.1

  Cross-aldolization of 3-O-benzyl-N-(benzyloxycarbonyl)-2,6,7-trideoxy-2,6-imino-4,5-O-isopropylidene-beta-D-glycero-L-mannoheptose ((-)- 12, derived from D-glycero-D-gulo-heptono-1,4-lactone in eight steps with (+)-(1R,4S,5S,6S)- and (-)-(1S,4R,5R,6R)-6-chloro-5-(phenylseleno)-7-oxabicyclo[2.2.1]heptan-2-one (obtained in one step from the ''naked sugars'' (-)- and (+)-7-oxabicyclo[2,2.1]hept-5-en-2-one) were highly stereoselective (lithium enolates, like modes, giving aldols (-)- 14 and (+)- 16, respectively. Stereoselective methods were developed for the conversion of(-)- 14 into methyl -imino-beta-D-glycero-L-manno-heptitol-1'-yl]-alpha and -beta-D-altro-furanoside ((+)-1 alpha,beta). The aza-C-disaccharide 1 alpha prefers a anti conformation (bonds C(2')-C(3') and C(1')-C(3) are antiperiplanar) for the beta-D-galactoside moiety ((3)J(H,H) coupling constants, NOEs). Aldol(+)- 16 was converted stereoselectively into 3-deoxy-3-C-[(1'S)-2',6',7'-trideoxy -2 D-glycero-L-manno-heptitol-1'-yl]-beta-D-galactose trifluoroacetate.