(4R,5R)-2,2-dimethyl-4-phenyl-5-vinyl-1,3-dioxolane | 145376-18-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4R,5R)-2,2-dimethyl-4-phenyl-5-vinyl-1,3-dioxolane
• 英文别名: trans-2,2-Dimethyl-4-phenyl-5-vinyl-1,3-dioxolan；(4R,5R)-4-ethenyl-2,2-dimethyl-5-phenyl-1,3-dioxolane
• CAS: 145376-18-7
• 化学式: C₁₃H₁₆O₂
• 分子量: 204.269
• InChiKey: QZAZBEJAECWYBL-VXGBXAGGSA-N

物化性质

• 沸点：
  285.2±28.0 °C(Predicted)
• 密度：
  1.051±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4R,5R)-2,2-dimethyl-4-phenyl-5-vinyl-1,3-dioxolane 在 二甲基硫 、 臭氧 作用下， 生成 (4S,5R)-2,2-Dimethyl-5-phenyl-1,3-dioxolan-4-carbaldehyde
  参考文献：
  名称：

  Kadota, Isao; Kobayashi, Katsumi; Okano, Hiroshi, Bulletin de la Societe Chimique de France, 1995, vol. 132, p. 615 - 623

  摘要：

  DOI：
• 作为产物：
  描述：

  2-<(Z)-3-(1-methoxy-1-methylethoxy)-2-propenyl>-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 对甲苯磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 (4R,5R)-2,2-dimethyl-4-phenyl-5-vinyl-1,3-dioxolane
  参考文献：
  名称：

  Hoffmann, Reinhard W.; Kemper, Bruno; Metternich, Rainer, Liebigs Annalen der Chemie, 1985, # 11, p. 2246 - 2260

  摘要：

  DOI：

文献信息

• Total synthesis of (±)-9-deoxygoniopypyrone. Application of the iodocyclofunctionalization reaction of bold α-allenic alcohol derivatives
  作者：Richard W Friesen、Suzanne Bissada

  DOI：10.1139/v97-212

  日期：1998.1.1

  The synthesis of ( ±)-9-deoxygoniopypyrone (1) from the α-allenic alcohol 5 is described. Iodocyclofunctionaliztion of the N-tosyl carbamate derivative of 5 using I₂ and Ag₂CO₃ provided, in a highly diastereoselective and regioselective fashion, the vinyl iodo syn-vicinal diol 4. Two routes were explored in order to introduce the third stereogenic centre in the molecule. Reductive deiodination of the vinyl iodide and diastereoselective epoxidation of the derived acetonide14 using mCPBA provided a mixture of epoxides 15 and 16 (2:1) in which the desired threo diastereomer predominated. Alternatively, dihydroxylation of acetonide 14 (OsO₄, NMO) yielded a mixture of diols 21 and 22 (2:3) which were separated after monosilylation (TBDMSCl) of the primary alcohol. The major silyl ether erythro diastereomer 24 was converted to the desired epoxide 15 by mesylation (MsCl, Et₃N) and epoxide formation (TBAF) with inversion of stereochemistry. The minor threo diastereomer 23 was also converted to the desired epoxide 15 (TBAF; ArSO₂Cl; NaOMe). Epoxide opening was effected with lithium acetylide and the resulting alkyne 27 was carbonylated (MeLi, ClCO₂Me) to afford the α , β-acetylenic ester 28. Semi hydrogenation over Lindlar's catalyst followed by protecting- group removal under acidic conditions provided ( ±)-8-epigoniodiol 30. Finally, conversion of 30 to ( ±)-9-deoxygoniopypyrone 1 was effected under basic conditions (DBU).Key words: ( ±)-9-deoxygoniopypyrone, α-allenic alcohol, iodocyclofunctionalization, syn-diol.

  合成（±）-9-去氧戈尼欧吡喃（1）从α-烯丙醇5的描述。使用I₂和Ag₂CO₃对5的N-对甲苯磺酰基衍生物进行碘环功能化，以高度顺式选择性和区域选择性的方式提供了乙烯碘同位二醇4。为了在分子中引入第三个立体异构中心，探索了两条途径。乙烯碘化物的还原去碘和衍生的乙酮酸酯14的顺式选择性环氧化使用mCPBA提供了环氧化物15和16的混合物（2:1），其中所需的threo对显性异构体占主导地位。另外，乙酮酸酯14的二羟基化（OsO₄，NMO）产生了二醇21和22的混合物（2:3），在初级醇的单硅基化（TBDMSCl）后分离。主要硅醚erythro对显性异构体24通过甲磺酰化（MsCl，Et₃N）和环氧化物形成（TBAF）转化为所需的环氧化物15，立体化学反应发生反转。次要threo对显性异构体23也转化为所需的环氧化物15（TBAF；ArSO₂Cl；NaOMe）。环氧化物开环作用于锂乙炔基，并且生成的炔烃27经羰基化（MeLi，ClCO₂Me）得到α，β-乙炔基酯28。在Lindlar催化剂上的半氢化，随后在酸性条件下去除保护基提供（±）-8-epigoniodiol 30。最后，将30转化为（±）-9-去氧戈尼欧吡喃1在碱性条件下进行（DBU）。关键词：（±）-9-去氧戈尼欧吡喃，α-烯丙醇，碘环功能化，顺式二醇。
• 3-Bromopropenyl Esters in Organic Synthesis:  Indium- and Zinc-Mediated Entries to Alk-1-ene-3,4-diols
  作者：Marco Lombardo、Stefano Morganti、Claudio Trombini

  DOI：10.1021/jo0262457

  日期：2003.2.1

  Metallic indium and zinc readily add to 3-bromopropenyl acetate (5) and benzoate (6) either in THF or in water, affording the corresponding 3-acyloxyallyl organometallic compounds. Nucleophilic addition to aldehydes opens a route to alk-1-ene-3,4-diols 2 in good to excellent yields. Two synthetic protocols were developed, the former involving indium in THF under Grignard conditions and the latter involving zinc in aqueous ammonium chloride under Barbier conditions. The diastereoselectivity, under all the conditions examined, mainly depends on the nature of the carbonyl compound; conjugated aldehydes afford syn adducts 2, while unconjugated aldehydes display the opposite anti stereopreference.
• Enantio- and Diastereoselective Synthesis of (<i>E</i>)-1,5-<i>syn</i>-Diols: Application to the Synthesis of the C(23)−C(40) Fragment of Tetrafibricin
  作者：Jeremy Kister、Philippe Nuhant、Ricardo Lira、Achim Sorg、William R. Roush

  DOI：10.1021/ol2003836

  日期：2011.4.1

  A highly stereoselective synthesis of (E)-1,5-syn-diols 6 Is described. The kinetically controlled hydroboration of allenyltrifluoroborate 8 with Soderquist borane 2 provides the (Z)-allylic trifluoroborate 9, which undergoes sequential allylboration with two different aldehydes to provide (E)-1,5-syn-diols 6 In 72-98% yields with > 95% ee and > 20:1 dr. Application of this method to the synthesis of the tetraflbricin C(23)-C(40) fragment 19 is described.
• Asymmetric synthesis of syn 1,2-diols via the reaction of aldehydes with chiral .gamma.-(tetrahydropyranyloxy)allylstannanes
  作者：Yoshinori Yamamoto、Katsumi Kobayashi、Hiroshi Okano、Isao Kadota

  DOI：10.1021/jo00052a002

  日期：1992.12

  Asymmetric synthesis of syn 1,2-diols 3 has been accomplished via the reaction of the chiral gamma-alkoxy-substituted allylstannane 1 with aldehydes in the presence of AlCl3 or AlCl3.OEt2, followed by a five-step operation to remove the chiral auxiliary.
• Total synthesis of (±)-9-deoxygoniopypyrone
  作者：Richard W. Friesen、Suzanne Bissada

  DOI：10.1016/s0040-4039(00)77261-3

  日期：1994.8

  The total synthesis of (+/-)-9-deoxygoniopypyrone (1) from the alpha-allenic alcohol 2 is described. The synthesis is accomplished in 10 steps with the relative configuration of the three contiguous asymmetric centers being established by the highly diastereoselective formation of the synvicinal diet 3 via the iodo-cyclofunctionalization reaction of the allenic carbamate 5 and the epoxidation of the olefinic acetonide 11.