tert-butyl 2''-methyl-2'',3''-dihydro-10H-dispiro[acridine-9,2'-thiirane-3',1''-benzo[f]thiochromene]-10-carboxylate | 1206461-95-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: tert-butyl 2''-methyl-2'',3''-dihydro-10H-dispiro[acridine-9,2'-thiirane-3',1''-benzo[f]thiochromene]-10-carboxylate
• CAS: 1206461-95-1
• 化学式: C₃₂H₂₉NO₂S₂
• 分子量: 523.72
• InChiKey: YMTICRDCHPFGEE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.85
• 重原子数：
  37.0
• 可旋转键数：
  0.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  29.54
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  tert-butyl 2''-methyl-2'',3''-dihydro-10H-dispiro[acridine-9,2'-thiirane-3',1''-benzo[f]thiochromene]-10-carboxylate 在 三(4-甲氧苯基)膦 作用下， 以 甲苯 为溶剂， 反应 16.0h， 以81%的产率得到tert-butyl 9-(2-methyl-2,3-dihydro-1H-benzo[f]thiochromen-1-ylidene)acridine-10(9H)-carboxylate
  参考文献：
  名称：

  An unexpected bidirectional molecular rotor from unidirectional molecular motor via a stereoselective enamine-imine tautomerization process

  摘要：

  Developing stereoselective synthetic method is very important to access chiral molecular devices. We herein demonstrate how a proton initiated stereoselective enamine-imine tautomerization converts a molecular motor into a simple rotor with high diastereoselectivity (>20:1 dr). NMR and X-ray crystallography were used to elucidate the structures of both the motor and rotor unambiguously. The activated motion of the rotor about its central single bond was studied from variable temperature NMR (293423 K) and DFT calculations provide evidence of the origin of diastereoselectivity of enamine-imine tautomerization as well as the rotor dynamics with barrier as high as 39.3 kcal/mol. Results from our work may benefit future design towards stereocontrolled and adaptive molecular machines. (C) 2020 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2020.152373
• 作为产物：
  描述：

  2,3-dihydro-2-methyl-1H-naphtho[2,1-b]thiopyran-1-one 在 manganese(IV) oxide 、 hydrazine hydrate 、 sodium sulfate 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 18.5h， 生成 tert-butyl 2''-methyl-2'',3''-dihydro-10H-dispiro[acridine-9,2'-thiirane-3',1''-benzo[f]thiochromene]-10-carboxylate
  参考文献：
  名称：

  An unexpected bidirectional molecular rotor from unidirectional molecular motor via a stereoselective enamine-imine tautomerization process

  摘要：

  Developing stereoselective synthetic method is very important to access chiral molecular devices. We herein demonstrate how a proton initiated stereoselective enamine-imine tautomerization converts a molecular motor into a simple rotor with high diastereoselectivity (>20:1 dr). NMR and X-ray crystallography were used to elucidate the structures of both the motor and rotor unambiguously. The activated motion of the rotor about its central single bond was studied from variable temperature NMR (293423 K) and DFT calculations provide evidence of the origin of diastereoselectivity of enamine-imine tautomerization as well as the rotor dynamics with barrier as high as 39.3 kcal/mol. Results from our work may benefit future design towards stereocontrolled and adaptive molecular machines. (C) 2020 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2020.152373

文献信息

• Ultrafast Light-Driven Nanomotors Based on an Acridane Stator
  作者：Artem A. Kulago、Emile M. Mes、Martin Klok、Auke Meetsma、Albert M. Brouwer、Ben L. Feringa

  DOI：10.1021/jo902207x

  日期：2010.2.5

  A series Of Molecular motors featuring a symmetrical acridane stator is reported. Photochemical and thermal isomerization experiments confirm that this stator, in combination with a thiopyran rotor, results in molecular rotary motion in which the rate-determining thermal helix inversion proceeds effectively only at temperatures above 373 K. The introduction of a cyclopentanylidene rotor unit results in a decrease in steric hindrance with respect to the stator, and as a consequence, a 10(12)-fold increase in the rate of thermal helix inversion is observed. Nanosecond transient absorption spectroscopy allows for the thermal processes to be followed accurately at ambient temperature. The rotary motor is shown to be able to operate at 0.5 MHz rotational frequencies Under optimal conditions.