(R)-(+)-1-(tert-butylsulfinyl)naphthalene | 203503-64-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (R)-(+)-1-(tert-butylsulfinyl)naphthalene
• 英文别名: (S)-(-)-1-(tert-butylsulfinyl)naphthalene；(S)-1-<(2-Methylprop-2-yl)sulfinyl>naphthalene；(S)-tert-butyl 1-naphthylsulfoxide；(S)-(-)-tert-butylsulfinyl-1-naphthalene；1-[(S)-tert-butylsulfinyl]naphthalene
• CAS: 203503-64-4
• 化学式: C₁₄H₁₆OS
• 分子量: 232.346
• InChiKey: KWEXAZRAXOUWEH-MRXNPFEDSA-N

物化性质

• 熔点：
  69 °C
• 沸点：
  398.6±11.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-(+)-1-(tert-butylsulfinyl)naphthalene 在 正丁基锂 、 1,1,2,2-四氟-1,2-二溴乙烷 作用下， 生成 (R)-(+)-2-bromo-1-(tert-butylsulfinyl)naphthalene
  参考文献：
  名称：

  Baker, Robert W.; Hockless, David C. R.; Pocock, Geoffrey R., Journal of the Chemical Society. Perkin transactions I, 1995, # 20, p. 2615 - 2630

  摘要：

  DOI：
• 作为产物：
  描述：

  sodium naphthalene-1-sulfinate 在 氯化亚砜 、 三乙胺 、 N,N-二甲基甲酰胺 、 三甲氧基磷 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 25.25h， 生成 (R)-(+)-1-(tert-butylsulfinyl)naphthalene
  参考文献：
  名称：

  Baker, Robert W.; Hockless, David C. R.; Pocock, Geoffrey R., Journal of the Chemical Society. Perkin transactions I, 1995, # 20, p. 2615 - 2630

  摘要：

  DOI：

文献信息

• New Asymmetric Reactions of 2-Formyl- and 2-Acyl-1-[(2,4,6-triisopropylphenyl)sulfinyl]naphthalenes via Diastereomeric Rotamers
  作者：Shuichi Nakamura、Hiroki Yasuda、Yoshihiko Watanabe、Takeshi Toru

  DOI：10.1021/jo005581p

  日期：2000.12.1

  Nucleophilic reactions with Grignard reagents and the Mukaiyama aldol reactions of the naphthaldehydes having the (2,4, 6-triisopropylphenyl)sulfinyl group produced products with high stereoselectivity. In these reactions, the stereochemistry of the major products changes depending on the Lewis acids used. Reduction of the 2-acyl-1-[(2,4,6-triisopropylphenyl)sulfinyl]naphthalenes also proceeds with

  用格氏试剂的亲核反应和具有（2,4,6-三异丙基苯基）亚磺酰基的萘醛的Mukaiyama aldol反应产生具有高立体选择性的产物。在这些反应中，主要产物的立体化学根据所使用的路易斯酸而变化。2-酰基-1-[[（2,4,6-三异丙基苯基）亚磺酰基]萘的还原也以高的立体选择性进行，但是根据还原剂的不同，其立体化学也不同。通过基于X射线晶体结构以及（1）H和（13）C NMR光谱数据的机理研究，我们证明了这些反应的极高和特定的立体选择性是由于周围的主要旋转异构体C（naph）-S轴。作为实例，提供对映体纯的2-萘甲醇的合成。
• Desymmetrization of Prochiral Diaryl Sulfoxides by an Asymmetric Sulfoxide-Magnesium Exchange
  作者：Thomas Hampel、Simon Ruppenthal、Daniel Sälinger、Reinhard Brückner

  DOI：10.1002/chem.201103928

  日期：2012.3.12

  The first desymmetrizations of prochiral diaryl sulfoxides 1 by an asymmetric sulfoxide–magnesium exchange reaction are reported. The respective substrate (1), iPr2Mg, and the dilithium salt of (S)‐BINOL (which was prepared in situ) provided (S)‐configured aryl isopropyl sulfoxides 2 in up to 91 % yield and with up to 91 % ee. (S)‐BINOL was re‐isolable in 98 % yield.

  据报道，前者通过不对称亚砜-镁交换反应使前手性二芳基亚砜1脱对称。相应的底物（1），i Pr 2 Mg和（S）-BINOL的二锂盐（原位制备）提供了（S）-配置的芳基异丙基亚砜2，产率高达91％，产率高达91 ％ee。（S）‐BINOL可重新分离，收率为98％。
• Conformational studies by dynamic NMR. 50. Atropisomerism in hindered naphthyl sulfoxides: structure, stereodynamics, and chiral resolution
  作者：D. Casarini、E. Foresti、F. Gasparrini、L. Lunazzi、D. Misiti、D. Macciantelli、C. Villani

  DOI：10.1021/jo00073a028

  日期：1993.10

  Barriers for the EZ interconversion of atropisomers of 1-naphthyl sulfoxides (ArSOR) having a methyl group at position 2 of the naphthalene moiety were measured by variable-temperature NMR. Their values were found to cover the range 10.6-18.4 kcal mol-1, the extreme values corresponding to derivatives 1 (R = Me) and 4 (R = Bu(t)), respectively. NOE and LIS measurements indicated that the Z atropisomer is more stable than the E but that the absence of the methyl group at position 2 of the naphthalene moiety reverses this trend, rendering E more stable than Z. Solid-state NMR and X-ray diffraction of 4 established that only the more stable atropisomer (Z) is present in the crystalline state. Molecular mechanics calculations suggest that the Z,E interconversion process might occur by a rotation pathway having an opposite direction in the case of the more hindered derivatives 3 and 4 (R = Pr(i) and Bu(t), respectively) with respect to the less hindered 1 and 2 (R = Me and Et, respectively). The enantiomers, which are due to the presence of the asymmetric sulfur atom, were resolved on a chiral stationary phase (DACH-DNB) having an SS configuration. Asymmetric oxidation reactions were employed to assign the absolute R configuration to the more retained enantiomers of alkyl aryl sulfoxides. The opposite trend (S being retained longer) was observed for diaryl sulfoxides such as 5 (R = Ph). In the case of the derivative with the largest interconversion barrier, sulfoxide 4, it was also possible to resolve (at -35-degrees-C) the two enantiomeric forms and their associated atropisomers. The use of on-line CD detection and the knowledge of the NMR assignments allowed us to unambiguously assign the elution order of the four species as ES, ER, ZS, ZR.
• <i>ortho</i>-Metalation of Enantiopure Aromatic Sulfoxides and Stereocontrolled Addition to Imines
  作者：Nicolas Le Fur、Ljubica Mojovic、Nelly Plé、Alain Turck、Vincent Reboul、Patrick Metzner

  DOI：10.1021/jo052358p

  日期：2006.3.31

  Enantiopure aromatic (phenyl, naphthyl) and heteroaromatic (pyridyl, quinolyl, diazinyl) sulfoxides have been synthesized by reaction of (S)-tert-butyl tert-butanethiosulfinate with aryl- or heteroaryllithium derivatives. The ortho-directed metalation of the sulfoxides was performed with lithium bases. Subsequent addition of the lithiated intermediates to N-tosylimines afforded tosylaminoalkyl tert-butylsulfinyl arenes. In most cases a complete asymmetric induction was highlighted in favor of (S,S) isomers. Heating the aminosulfoxides provided an original cyclization to form novel cyclic sulfenamides. A novel enantiopure synthesis of a benzylamine was described. An application of an enantiopure aminosulfoxide as N,S ligand for the asymmetric catalysis of allylic nucleophilic substitution has been successfully tested.
• BINOL derived C2-symmetric bis-sulfinates as efficient sulfinyl transfer agents in the synthesis of tert-butyl sulfoxides
  作者：N. Gaggero、D.C.M. Albanese

  DOI：10.1016/j.tet.2012.06.050

  日期：2012.9

  The reaction of novel C-2-symmetric bis-sulfinate esters derived from (R)-BINOL with Grignard reagents affords tert-butyl sulfoxides in ee up to 97%. The desired enantiomer can be generated at will by the proper selection of BINOL (C) 2012 Elsevier Ltd. All rights reserved.