1-(phenylsulfinyl)-2,2,2-triethoxyethane | 127492-03-9

• 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: 1-(phenylsulfinyl)-2,2,2-triethoxyethane
• 英文别名: 2-(Phenylsulfinyl)-1,1,1-triethoxyethane；(Triethylphenyl)sulfinyl orthoacetate；Benzene, [(2,2,2-triethoxyethyl)sulfinyl]-；2,2,2-triethoxyethylsulfinylbenzene
• CAS: 127492-03-9
• 化学式: C₁₄H₂₂O₄S
• 分子量: 286.392
• InChiKey: TXCOFLIGKXNVKM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  19
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  64
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-丁烯-2-醇 、 1-(phenylsulfinyl)-2,2,2-triethoxyethane 在 氢气 作用下， 以79%的产率得到ethyl hexa-2,4-dienoate
  参考文献：
  名称：

  Asymmetric total synthesis of an A-ring precursor to hormonally active 1.alpha.,25-dihydroxyvitamin D3

  摘要：

  DOI：

  10.1021/jo00300a001
• 作为产物：
  描述：

  2,2,2-三氯乙基苯基硫化物 在 间氯过氧苯甲酸 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 1-(phenylsulfinyl)-2,2,2-triethoxyethane
  参考文献：
  名称：

  One-flask, regiospecific conversions of allylic alcohols into 2-carbon-extended, conjugated dienoate esters. Use of a new sulfinyl orthoester

  摘要：

  Sixteen differently substituted primary and secondary allylic alcohols are shown to react with sulfinyl orthoacetate 1 at 100-degrees-C sequentially via a [3,3] sigmatropic rearrangement and then a beta-elimination of benzenesulfenic acid to form conjugated dienoate esters 5-13 in 45-95% yields. This one-flask, intramolecular carbon-carbon bond-forming process represents a simple and convenient method for regiospecific gamma-attachment of a two-carbon (ethoxycarbonyl)methylene unit via the synthetic equivalent of an S(N)2' process. Two examples are given in which rationally designed dienoates 20 and 24, prepared via this one-flask process and carrying a pendant alkene unit, undergo intramolecular 2 + 4 cycloaddition producing bicyclic cyclohexenes 21 and 25.

  DOI：

  10.1021/jo00025a008

文献信息

• New vitamin D3 derivatives with unexpected antiproliferative activity: 1-(hydroxymethyl)-25-hydroxyvitamin D3 homologs
  作者：Gary H. Posner、Todd D. Nelson、Kathryn Z. Guyton、Thomas W. Kensler

  DOI：10.1021/jm00095a026

  日期：1992.8

  Surprisingly, both of the synthetic 1-(hydroxymethyl)-25-hydroxyvitamin D3 diastereomers (-)-2 and (+)-3 retained the antiproliferative activity of natural calcitriol in murine keratinocytes. Preliminary studies indicated, however, that both of these synthetic diastereomers were less than 0.1% as effective as calcitriol for binding to the 1,25-(OH)2-D3 receptor and that they were less than 0.1% as

  令人惊讶地，合成的1-（羟甲基）-25-羟基维生素D3非对映异构体（-）-2和（+）-3均保留了天然骨化三醇在鼠角质形成细胞中的抗增殖活性。然而，初步研究表明，这两种合成的非对映异构体与钙三醇结合1,25-（OH）2-D3受体的有效性均低于钙三醇，而钙结合蛋白的效价均低于钙三醇的0.1％。器官培养的胚胎十二指肠中的-D28K诱导。1-（羟甲基）-25-羟基维生素D3同源物（-）-2和（+）-3通过对映体纯的C，D环酮12与高度对映体富集的A环膦氧化物（- ）-11a和（+）-11b。从3-溴-2-吡喃酮和丙烯醛的热[2 + 4]环加成反应开始制备这些A环螯合物。
• Antiproliferative Hybrid Analogs of the Hormone 1α,25-Dihydroxyvitamin D₃:  Design, Synthesis, and Preliminary Biological Evaluation
  作者：Gary H. Posner、Jae Kyoo Lee、M. Christina White、Richard H. Hutchings、Haiyan Dai、Joseph L. Kachinski、Patrick Dolan、Thomas W. Kensler

  DOI：10.1021/jo970049w

  日期：1997.5.1

  dichloride promotes highly regioselective and stereoselective Diels-Alder cycloaddition between 3-bromo-2-pyrone, prepared in a new way, and unactivated terminal alkene 4-(tert-butyldimethylsiloxy)-1-butene. The conjugate base of A-ring allylic phosphine oxide 20 adds chemospecifically to the C-8 keto group of some C-8,C-24-diketones to form directly metabolically resistant 24-oxo analogs of 1alpha,25-dihydroxyvitamin

  10-12 kbar压力与Lewis酸性二氯化锌的结合促进了以新方法制备的3-溴-2-吡喃酮与未活化的末端烯烃4-（叔丁基二甲基甲硅烷氧基）-1之间的高度区域选择性和立体选择性Diels-Alder环加成反应-丁烯。A环烯丙基氧化膦20的共轭碱将化学特异性地添加到某些C-8，C-24-二酮的C-8酮基上，从而直接形成1alpha，25-dihydroxyvitamin D（3）的具有抗新陈代谢作用的24-oxo类似物。 （骨化三醇）。这些新的杂合类似物中的几种在体外抑制钙质细胞生长的作用与钙三醇一样，即使在生理上相关的10-100纳摩尔浓度下也是如此。
• New A-ring analogs of the hormone 1α,25-dihydroxyvitamin D3: (2′-hydroxymethyl)tetrahydrofuro[1,2-a]-25-hydroxyvitamin D3
  作者：Heung Bae Jeon、Gary H. Posner

  DOI：10.1016/j.tet.2008.12.034

  日期：2009.2

  and (S)- or (R)-2-(tert-butyldimethylsilyloxy)methyl-2,3-dihydrofuran, respectively. In addition, (2′-hydroxymethyl)tetrahydrofuro[1,2-a]-25-hydroxyvitamin D3 3a and 3b as new A-ring-modified analogs of the natural hormone 1α,25-dihydroxyvitamin D3 were readily synthesized by using Lythgoe-type coupling of the A-ring phosphine oxides (+)-4 and (−)-4 with C,D-ring ketone (+)-5.

  从概念上讲，新的对映体纯净的双环四氢呋喃并[1,2 - a ] -A-环氧化膦（+）- 4和（-）- 4从2-pyrone-3-羧酸甲酯和（S）-或（R）-2-（叔丁基二甲基甲硅烷氧基）甲基-2,3-二氢呋喃。此外，（2'-羟甲基）四氢呋喃并[1,2一] -25羟基维生素d 3 图3a和3b中作为天然激素1α的新的A-环改性类似物，25-二羟基维生素d 3通过使用被容易地合成A环氧化膦（+）- 4和（-）- 4的Lygogoe型偶联带有C，D环酮（+）- 5。
• Asymmetric Synthesis of Vitamin D₃ Analogues: Organocatalytic Desymmetrization Approach toward the A-Ring Precursor of Calcifediol
  作者：Haifeng Wang、Linjie Yan、Yan Wu、Yipei Lu、Fener Chen

  DOI：10.1021/acs.orglett.5b02813

  日期：2015.11.6

  A novel asymmetric synthesis has been developed for the construction of the A-ring of a chiral precursor to calcifediol. The highlights of this synthesis include (i) the introduction of the stereochemistry at the C5-position of the A-ring through the organocatalytic enantioselective desymmetrization of a prochiral cyclic anhydride using a bifunctional urea catalyst and (ii) the introduction of the

  已经开发了一种新颖的不对称合成物，用于构建牙本质二醇的手性前体的A环。该合成的亮点包括：（i）引入在A环的C5位的立体化学通过的前手性环酐使用的双功能催化剂的尿素和（ii）在引入有机催化的对映选择性desymmetrization外型-环（Z）-二烯醇侧链通过烯丙基醇的串联克莱森重排/亚砜热解。
• Stereocontrolled Total Synthesis of Calcitriol Derivatives: 1,25-Dihydroxy-2-(4'-hydroxybutyl)vitamin D3 Analogs of an Osteoporosis Drug
  作者：Gary H. Posner、Neil Johnson

  DOI：10.1021/jo00104a050

  日期：1994.12

  The diastereomeric 2 alpha- and 2 beta-(4'-hydroxybutyl) calcitriol analogs (-)-3 and (+)-3' were prepared in only 11 chemical operations, starting with 4 + 2-cycloaddition of commercially available methyl 2-pyrone-3-carboxylate. Highlights of this convergent and stereocontrolled synthetic approach are as follows: (1) retention of reactant dienophile geometry in the product bicyclic lactone, characteristic of a concerted inverse-electron-demand Diels-Alder cycloaddition; (2) an improved decarboxylation procedure involving chemospecific allyloxide opening of a lactone ring in the presence of a methyl ester and then non-high pressure palladium-promoted allylic ester decarboxylation; and (3) use of the enantiomercially pure C,D-ring chiron (+)-14 to resolve racemic A-ring phosphine oxide (+/-)-13. Relative binding affinities of the enantiomerically pure diastereomers (-)-3 and (+)-3' to the vitamin D binding protein and to the vitamin D receptor showed some unexpected trends. Diastereomer (+)-3' surprisingly bound more effectively to the vitamin D receptor than did the established osteoporosis drug ED-71 (1).