(3aS,8aS)-hexahydro-2,2-dimethyl-4,4,8,8-tetraphenyl-6H-1,3-dioxolo[4,5-e][1,3]diazepine-6-thione | 1399830-18-2

• 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: (3aS,8aS)-hexahydro-2,2-dimethyl-4,4,8,8-tetraphenyl-6H-1,3-dioxolo[4,5-e][1,3]diazepine-6-thione
• 英文别名: (3aS,8aS)-2,2-dimethyl-4,4,8,8-tetraphenyl-3a,5,7,8a-tetrahydro-[1,3]dioxolo[4,5-e][1,3]diazepine-6-thione
• CAS: 1399830-18-2
• 化学式: C₃₂H₃₀N₂O₂S
• 分子量: 506.668
• InChiKey: PXAQMZMJKVXFIM-VSGBNLITSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  37
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  74.6
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3aS,8aS)-hexahydro-2,2-dimethyl-4,4,8,8-tetraphenyl-6H-1,3-dioxolo[4,5-e][1,3]diazepine-6-thione 在 potassium carbonate 、 copper(l) chloride 、 sodium hydroxide 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 2.17h， 生成 (3aS,8aS)-N-[(4-chlorophenyl)methyl]-2,2-dimethyl-4,4,8,8-tetraphenyl-3a,5,7,8a-tetrahydro-[1,3]dioxolo[4,5-e][1,3]diazepin-6-imine
  参考文献：
  名称：

  Development of Tartaric Acid Derived Chiral Guanidines and Their Application to Catalytic Enantioselective α-Hydroxylation of β-Dicarbonyl Compounds

  摘要：

  A novel library of chiral guanidines featuring a tartaric acid skeleton was developed from diethyl L-tartrate. These guanidines are easily accessed with tunable style and electronic properties. The utilities of the guanidines were highlighted by their ability to catalyze the alpha-hydroxylation of beta-ketoesters and beta-diketones with remarkable efficiency and excellent enantioselectivity.

  DOI：

  10.1021/ol401306h
• 作为产物：
  描述：

  (-)-二甲基-2,3-邻异丙亚基-L-酒石酸酯 在 lithium aluminium tetrahydride 、 氯化亚砜 、 magnesium 、 三乙胺 作用下， 以 四氢呋喃 、 吡啶 、 二氯甲烷 为溶剂， 反应 87.5h， 生成 (3aS,8aS)-hexahydro-2,2-dimethyl-4,4,8,8-tetraphenyl-6H-1,3-dioxolo[4,5-e][1,3]diazepine-6-thione
  参考文献：
  名称：

  Development of Tartaric Acid Derived Chiral Guanidines and Their Application to Catalytic Enantioselective α-Hydroxylation of β-Dicarbonyl Compounds

  摘要：

  A novel library of chiral guanidines featuring a tartaric acid skeleton was developed from diethyl L-tartrate. These guanidines are easily accessed with tunable style and electronic properties. The utilities of the guanidines were highlighted by their ability to catalyze the alpha-hydroxylation of beta-ketoesters and beta-diketones with remarkable efficiency and excellent enantioselectivity.

  DOI：

  10.1021/ol401306h

文献信息

• Preparation and Characterization of New C2- and C1-Symmetric Nitrogen, Oxygen, Phosphorous, and Sulfur Derivatives and Analogs of TADDOL. Part II
  作者：Arkadius Pichota、Volker Gramlich、Hans-Ulrich Bichsel、Thomas Styner、Thomas Knöpfel、Ralf Wünsch、Tobias Hintermann、W. Bernd Schweizer、Albert K. Beck、Dieter Seebach

  DOI：10.1002/hlca.201200147

  日期：2012.8

  α′,α′‐tetraphenyl‐1,3‐dioxolan‐4,5‐dimethanamines) (Scheme 2) and ureas, 12–15, and to TADDOP derivatives with seven‐membered OPO ester rings (Schemes 3 and 4). Cl/P‐Replacement via the MichaelisArbuzov reaction (Scheme 7) on mono‐ and dichlorides, derived from TADDOL, are described. It was not possible to obtain phosphines with the P‐atom attached to the benzhydrylic C‐atom of the TADDOL skeleton

  TADDOL（= α，α，α' ，α' -Tetraaryl -1,3-二氧戊环-4,5-二甲醇）和相应的二氯化物被转化成TADDAMINs（=（4小号，5小号）-2,2，Ñ，N'-四甲基-α，α，α'，α'-四苯基-1,3-二氧杂戊基4,5-二甲胺（方案2）和脲12至15以及具有七元O的TADDOP衍生物 P  0酯环（方案3和4）。Cl / P-替换通过的米氏阿尔布佐夫反应（方案7上的单-和二氯化物），从TADDOL衍生，进行说明。无法获得P原子连接到TADDOL骨架的二羟基C原子上的膦（方案6和7）。讨论了30多种新的TADDOL衍生物中的10种的X射线晶体结构（图1和2）。提供了完整的实验细节。
• Novel tartrate-derived guanidine-catalyzed highly enantio- and diastereoselective Michael addition of 3-substituted oxindoles to nitroolefins
  作者：Liwei Zou、Xiaoze Bao、Yuanyuan Ma、Yuming Song、Jingping Qu、Baomin Wang

  DOI：10.1039/c4cc01817f

  日期：——

  The Michael addition of 3-substituted oxindoles to nitroolefins was catalyzed by a novel tartrate-derived guanidine in high yield with excellent diastereo- and enantioselectivity. This method showed an extraordinarily broad substrate scope in terms of both reaction partners.

  3-取代的氧吲哚与硝基烯烃的迈克尔加成反应在一种新型的酒石酸衍生的胍的催化下，以高产率和优异的非对映选择性及手性选择性进行。该方法在反应底物方面显示出了极其广泛的适用性。
• Novel Tartrate-Based Guanidines for Enantioselective Fluorination of 1,3-Dicarbonyl and α-Cyano Carbonyl Compounds
  作者：Liwei Zou、Xiaoze Bao、Huanrui Zhang、Yuming Song、Jingping Qu、Baomin Wang

  DOI：10.1071/ch14179

  日期：——

  electronic properties. A guanidine molecule of this library with an incorporated 2,6-diisoaniline fragment was identified as a suitable promoter for the enantioselective fluorination of 1,3-dicarbonyl and α-cyano carbonyl compounds to furnish the fluorinated product with up to 84 % ee and 99 % yield using N-fluorobenzenesulfonimide (NFSI) as the fluorinating agent.

  具有酒石酸骨架的新型手性胍库具有可调节的空间和电子特性，可轻松访问。该文库中掺入2，6-二异苯胺片段的胍分子被鉴定为1,3-二羰基和α-氰基羰基化合物的对映选择性氟化的合适促进剂，可为氟化产物提供84％ee和99使用N-氟苯磺酰亚胺（NFSI）作为氟化剂的收率（％）。
• An Organocatalytic Asymmetric Friedel–Crafts Addition/Fluorination Sequence: Construction of Oxindole–Pyrazolone Conjugates Bearing Vicinal Tetrasubstituted Stereocenters
  作者：Xiaoze Bao、Baomin Wang、Longchen Cui、Guodong Zhu、Yuli He、Jingping Qu、Yuming Song

  DOI：10.1021/acs.orglett.5b02470

  日期：2015.11.6

  A highly efficient and practical one-pot sequential process, consisting of an organocatalytic enantioselective Friedel–Crafts-type addition of 4-nonsubstituted pyrazolones to isatin-derived N-Boc ketimines and a subsequent diastereoselective fluorination of the pyrazolone moiety, is developed. This reaction sequence delivers novel oxindole–pyrazolone adducts featuring vicinal tetrasubstituted stereocenters

  开发了一种高效实用的一锅法连续方法，该方法包括将4-未取代的吡唑啉酮有机催化对映选择性的Friedel-Crafts型加成至衍生自靛红的N -Boc酮亚胺，随后对吡唑啉酮部分进行非对映选择性氟化。该反应顺序可提供新颖的羟吲哚-吡唑啉酮加合物，其具有邻位四取代的立构中心，催化剂负载量为0.5 mol％，且对映体和非对映体控制出色。值得注意的是，氯，溴和硫醚官能团可以很容易地掺入，从而使产物具有广泛的多样性。
• Identification of a tartrate-based modular guanidine towards highly asymmetric Michael addition of 3-aminooxindoles to nitroolefins
  作者：Shiqiang Wei、Xiaoze Bao、Shah Nawaz、Jingping Qu、Baomin Wang

  DOI：10.1016/j.tetlet.2020.152741

  日期：2021.2