(4R,5R)-N⁴,N⁴,N⁵,N⁵,2,2-hexamethyl-1,3-dioxolane-4,5-dicarboxamide | 6134-83-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4R,5R)-N⁴,N⁴,N⁵,N⁵,2,2-hexamethyl-1,3-dioxolane-4,5-dicarboxamide
• 英文别名: (4R,5R)-2,2-dimethyl-1,3-dioxalane-4,5-dicarboxamide；(4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-dicarboxamide；(4R,5R)-2,2-dimethyl-4,5-dicarbamoyl-1,3-dioxolane；2,3-O-Isopropylidene-L-tartaramide
• CAS: 6134-83-4；6135-81-5；89852-20-0；97747-55-2
• 化学式: C₇H₁₂N₂O₄
• 分子量: 188.183
• InChiKey: YQPBXKXVZURPHT-QWWZWVQMSA-N

物化性质

• 沸点：
  483.7±45.0 °C(Predicted)
• 密度：
  1.288±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.6
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  105
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4R,5R)-N⁴,N⁴,N⁵,N⁵,2,2-hexamethyl-1,3-dioxolane-4,5-dicarboxamide 在 苯磺酰氯 作用下， 以 吡啶 为溶剂， 以80.5%的产率得到(-)-(4S,5S)-2,2-dimethyl-[1,3]-dioxolane-4,5-dicarbonitrile
  参考文献：
  名称：

  由（2 R，3 R）-酒石酸合成4-羟基-2,5-二甲基呋喃-3（2 H）-一（呋喃醇）

  摘要：

  （2R，3R）-酒石酸（6）已通过五步转换成重要的挥发性风味和香气成分4-羟基-2,5-二甲基呋喃-3（2 H）-一（呋喃酚）（1），总收率为18.5％。关键步骤涉及通过氯化甲基镁与相应的4,5-双（二甲基酰胺）的反应形成（4 R，5 R）-4,5-二乙酰基-2,2-二甲基-1,3-二氧戊环（10） ）。还通过涉及在相应的二腈上的格氏（Grignard）型反应的相关反应序列，也制备了相同的二氧戊环（10）。

  DOI：

  10.1039/p19850000795
• 作为产物：
  描述：

  (4R,5R)-4,5-二乙氧基羰基-2,2-二甲基二氧 在 氨 作用下， 以 甲醇 为溶剂， 生成 (4R,5R)-N⁴,N⁴,N⁵,N⁵,2,2-hexamethyl-1,3-dioxolane-4,5-dicarboxamide
  参考文献：
  名称：

  在相转移反应中开发新型不对称两中心催化剂

  摘要：

  设计了一种新的不对称两中心相转移催化剂，并建立了包含40多种新的两中心催化剂的催化剂库。将催化剂用于相转移烷基化和迈克尔加成中，以分别提供至多93％ee和82％ee的相应产物。

  DOI：

  10.1016/s0040-4039(02)02416-4

文献信息

• The Stereoisomeric Diaminobutanediol and Dioxadiazadecalin Systems: Synthesis, Structure, Stereoelectronics, and Conformation – Theory vs. Experiment
  作者：Alexander Star、Israel Goldberg、N. Gabriel Lemcoff、Benzion Fuchs

  DOI：10.1002/(sici)1099-0690(199909)1999:9<2033::aid-ejoc2033>3.0.co;2-k

  日期：1999.9

  We present new approaches to the (C2) chiral and meso 1,4-diamino-2,3-butanediol (1) and 2,3-diamino-1,4-butanediol (2) and derivatives. Reactions of these compounds with aldehydes to form the novel 1,5-dioxa-3,7-diazadecalin (DODAD) and 1,5-diaza-3,7-dioxadecalin (DADOD) classes of compounds (7, 9, 11–15) are also reported. These reactions are diastereospecific, i.e., erythro (meso) or threostarting

  我们提出了 (C2) 手性和内消旋 1,4-二氨基-2,3-丁二醇 (1) 和 2,3-二氨基-1,4-丁二醇 (2) 及其衍生物的新方法。这些化合物与醛反应形成新型 1,5-二氧杂-3,7-二氮杂萘 (DODAD) 和 1,5-二氮杂-3,7-二恶烷 (DADOD) 类化合物 (7, 9, 11–15) ) 也有报道。这些反应是非对映特异性的，即赤型（内消旋）或苏型起始化合物分别产生反式或顺式产物。这些系统的结构、构象和立体电子方面通过实验和计算进行了探索，并提供了对它们的特性和行为的深入了解。在 X 射线、NMR 和反式 DODAD (14) 和反式 DADOD (15) 的 N,N'-二苄基衍生物的计算结果之间观察到良好的一致性。
• Catalytic asymmetric phase-transfer reactions using tartrate-derived asymmetric two-center organocatalysts
  作者：Takashi Ohshima、Tomoyuki Shibuguchi、Yuhei Fukuta、Masakatsu Shibasaki

  DOI：10.1016/j.tet.2004.05.120

  日期：2004.8

  was used in phase-transfer alkylations and Michael additions to afford various optically active α-amino acid equivalents in up to 93% yield. Moreover, dramatic counter anion effects were observed in phase-transfer catalysis (PTC) for the first time, making it possible to further improve reactivity and selectivity. These findings validate the usefulness of three-dimensional fine-tuning of the catalyst

  设计了一种新的高度通用的不对称两中心催化剂，酒石酸衍生的二铵盐（TaDiAS），并构建了包含70多种新的两中心催化剂的催化剂库。各种（S，S）-和（R，R在操作简单的反应条件下，使用常规和廉价的试剂，可以分别分别从l-酒石酸二乙酯和d-酒石酸二乙酯合成）-TaDiAS。TaDiAS用于相转移烷基化和Michael加成反应，以高达93％的收率提供各种旋光性α-氨基酸当量。此外，首次在相转移催化（PTC）中观察到了显着的抗衡阴离子作用，从而有可能进一步提高反应性和选择性。这些发现证实了对催化剂（乙缩醛，Ar和抗衡阴离子）进行三维微调以进行优化的有用性。使用简单的程序也可以回收和再利用催化剂。本不对称PTC已成功地应用于丝氨酸蛋白酶抑制剂铜绿蛋白酶298-A及其类似物的对映选择性合成。
• Design, Synthesis, and Biological Evaluation of Novel Hybrid Dicaffeoyltartaric/Diketo Acid and Tetrazole-Substituted <scp>l</scp>-Chicoric Acid Analogue Inhibitors of Human Immunodeficiency Virus Type 1 Integrase
  作者：David C. Crosby、Xiangyang Lei、Charles G. Gibbs、Brenda R. McDougall、W. Edward Robinson、Manfred G. Reinecke

  DOI：10.1021/jm1010594

  日期：2010.11.25

  Fourteen analogues of the anti-HIV-1 integrase (IN) inhibitor L-chicoric acid (L-CA) were prepared. Their IC50 values for 3'-end processing and strand transfer against recombinant HIV-1 IN were determined in vitro, and their cell toxicities and EC50 against HIV-1 were measured in cells (ex vivo). Compounds 1-6 are catechol/beta-diketoacid hybrids, the majority of which exhibit submicromolar potency against 3'-end processing and strand transfer, though only with modest antiviral activities. Compounds 7-10 are L-CA/p-fluorobenzylpyrroloyl hybrids, several of which were more potent against strand transfer than 3'-end processing, a phenomenon previously attributed to the beta-diketo acid pharmacophore. Compounds 11-14 are tetrazole bioisosteres of L-CA and its analogues, whose in vitro potencies were comparable to L-CA but with enhanced antiviral potency. The trihydroxyphenyl analogue 14 was 30-fold more potent than L-CA at relatively nontoxic concentrations. These data indicate that L-CA analogues are attractive candidates for development into clinically relevant inhibitors of HIV-1 IN.
• ——
  作者：B. A. Shainyan、M. V. Ustinov、V. K. Bel'skii、L. O. Nindakova

  DOI：10.1023/a:1015367111704

  日期：——

  Chiral diamines having a C-2 symmetry, (4S,5S)-2,2-dimethyl-4,5-bis(aminomethyl)-1,3-dioxolane and (5S,5'S)-2,2,2',2'-tetramethyl-3,3'-diphenyl-5,5'-bioxazolidine, were synthesized on the basis of (+)-(2R,3R)-tartaric acid. Their structure was proved by X-ray analysis. The products were used as ligands in rhodium catalyst for enantioselective hydrogenation of alpha-acetamidocinnamic and itaconic acids.
• Asymmetric hydrogen-transfer hydrogenation on rhodium(I) complexes with new optically active salen ligands derived from (4S,5S)-4,5-bis(aminomethyl)-2,2-dimethyl-1,3-dioxolane
  作者：L. O. Nindakova、B. A. Shainyan、N. M. Badyrova、F. M. Lebed’

  DOI：10.1134/s1070428012010083

  日期：2012.1

  New optically active C-2-symmetric salen-type ligands were synthesized on the basis of (4S,5S)-4,5-bis(aminomethyl)-2,2-dimethyl-1,3-dioxolane. These ligands were used to obtain cationic (tri-fluoromethanesulfonate) and neutral (chloride) rhodium(I) complexes with [(4S,5S)-2,2-dimethyl-5-[(E)-pyridin-2-ylmethylidene]aminomethyl}-1,3-dioxolan-4-yl]-N-[(E)-pyridin-2-ylmethylidene]methanamine and [2,2-dimethyl-5-[(E)-quinolin-2-ylmethylidene]aminomethyl}-1,3-dioxolan-4-yl]-N-[(E)-quinolin-2-yl-methylidene]methanamine. The latter complex ensured preparation of (S)-2-phenylethanol with an optical yield of 34.8% by transfer hydrogenation of acetophenone.