(2S,3R,4S)-2,4-dimethyl-5-hexene-1,3-diol | 108817-24-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (2S,3R,4S)-2,4-dimethyl-5-hexene-1,3-diol
• 英文别名: (2S,3R,4S)-2,4-dimethylhex-5-ene-1,3-diol
• CAS: 108817-24-9
• 化学式: C₈H₁₆O₂
• 分子量: 144.214
• InChiKey: XHWFEANINCTWNL-BIIVOSGPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,3R,4S)-2,4-dimethyl-5-hexene-1,3-diol 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 甲酸 、 草酰氯 、 sodium hydride 、 臭氧 、 二甲基亚砜 、 三苯基膦 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 98.33h， 生成 (2R,3S,4R,5R)-5-[tert-butyl(dimethyl)silyl]oxy-2,4-dimethyl-3-phenylmethoxyheptanal
  参考文献：
  名称：

  9-二氢赤藓内酯B衍生物和赤藓内酯B的全合成

  摘要：

  (-)-erythronolide B (5) 及其两种 9-二氢衍生物（52 和 54）来自 (R)-2,3-O-异亚丙基甘油醛 (20) 的收敛全合成（最长线性路线上的 22 步）作为手性的唯一来源被描述。A key step of the synthesis is the regio- and stereocontrolled coupling of the allyl sulfide anion 39 and ketone 26 which can be directed to either α-adduct 40 or 41 by an appropriate choice of the conditions (Scheme V, table II). 由40和41制备seco酸47和49，根据改进的Yamaguchi程序将其顺利地大环内酯化为50和51。在大环立体控制下进行 50

  DOI：

  10.1021/ja00003a026
• 作为产物：
  描述：

  (2S,3R,4S)-1-(tert-butyldimethylsilyloxy)-2,4-dimethylhex-5-en-3-ol 在 四丁基氟化铵 作用下， 生成 (2S,3R,4S)-2,4-dimethyl-5-hexene-1,3-diol
  参考文献：
  名称：

  完全取代的含γ-吡喃酮的天然产物的合成研究：甲壳三酚II的首次全合成

  摘要：

  描述了甲壳三醇II（一种软体动物Onchidium sp。的细胞毒性代谢产物）的第一个全合成。它采用温和的环化方法[DMSO-（COCl）2或Ph 3 P-CCl 4 ]，将带有光学活性官能团的三酮化合物与相应的γ-吡喃酮类化合物结合在一起，作为关键步骤。一些非对映异构体的额外合成提供了修改紧密相关的甲壳三酚I结构的可能性。

  DOI：

  10.1016/0040-4039(94)88516-8

文献信息

• Beyond the Roche Ester: A New Approach to Polypropionate Stereotriad Synthesis
  作者：Corinne N. Foley、James L. Leighton

  DOI：10.1021/ol500051e

  日期：2014.2.21

  An efficient, step-economical, and scalable approach to the synthesis of polypropionate stereotriads has been developed. Either 2-butyne or propyne is subjected to rhodium-catalyzed silylformylation and in situ crotylation of the resulting aldehydes. Tamao oxidation under either “standard” conditions or “aprotic” conditions then delivers the completed stereotriads in a three-step, two-pot sequence

  已开发出一种高效、经济且可扩展的方法来合成聚丙酸酯立体三联体。2-丁炔或丙炔经过铑催化的甲硅烷基甲酰化和所得醛的原位巴豆化。Tamao 在“标准”条件或“非质子”条件下氧化，然后以三步两锅的顺序提供完整的立体三联体。与经典的罗氏酯方法相比，α-立体中心是“免费”获得的。
• Enantioselective and Diastereoselective Additions of Allylic Stannanes to Aldehydes Promoted by a Chiral (Acyloxy)borane Catalyst
  作者：James A. Marshall、Michael R. Palovich

  DOI：10.1021/jo980145c

  日期：1998.6.1

  A modified Yamamoto Lewis acid (CAB), prepared from the 2,6-dimethoxybenzoic ester of (R-R)-tartaric acid, and 1.5 equiv of BH3.THF was employed in additions of crotyltributyltin (6) and allyltributyltin (9) to representative achiral aldehydes in the presence of 2 equiv of (CF3CO)(2)O. The crotyltin additions proceeded with good to excellent diastereoselectivity and enantioselectivity affording the syn adducts 7a-e of 70-90% ee as major products (78:22-92:8). Addition of allylstannane 9 to cyclohexanecarboxaldehyde (1a) afforded the (R)-adduct of only 55% ee. In contrast, the use of Keck's BINOL catalyst gave 10, the allyl adduct of la, of 87% ee. However, addition of the crotylstannane to 1a with this catalyst led to a 65:35 mixture of syn and anti adducts 7a and 8a of 95% and 49% ee. Additions of crotylstannane 6 to (R)- and (S)-2-methyl-3-ODPS-propanal [(R)-11 and (S)-11] promoted by the modified CAB Lewis acid afforded the syn,syn and syn,anti products 12 and 14 in large predominance (98:2 and 90:10), indicative of effective complex control in the transition state. The results are consistent with the Corey H-bonded aldehyde transition-state proposal.
• Practical synthesis of diastereomerically and enantiomerically pure 2-methyl 1,3-diols from (R)-2,3,O-isopropylideneglyceraldehyde. Application to the C(1)-C(7) and C(9)-C(12) fragments of erythronolide B
  作者：Johann Mulzer、Leonore Autenrieth-Ansorge、Holger Kirstein、Toshikazu Matsuoka、Winfried Muench

  DOI：10.1021/jo00226a011

  日期：1987.8
• Synthetic studies on fully substituted γ-pyrone-containing natural products: The first total synthesis of onchitriol II
  作者：Hirokazu Arimoto、Shigeru Nishiyama、Shosuke Yamamura

  DOI：10.1016/0040-4039(94)88516-8

  日期：1994.12

  The first total synthesis of onchitriol II, a cytotoxic metabolite of mollusc Onchidium sp., is described. It employs mild cyclization method [DMSO - (COCl)2 or Ph3P - CCl4] of triketides bearing optically active functional groups to the corresponding γ-pyrones as a key step. Additional synthesis of some diastereoisomers provided a possibility to revise the structure of closely related onchitriol I.

  描述了甲壳三醇II（一种软体动物Onchidium sp。的细胞毒性代谢产物）的第一个全合成。它采用温和的环化方法[DMSO-（COCl）2或Ph 3 P-CCl 4 ]，将带有光学活性官能团的三酮化合物与相应的γ-吡喃酮类化合物结合在一起，作为关键步骤。一些非对映异构体的额外合成提供了修改紧密相关的甲壳三酚I结构的可能性。
• Total synthesis of 9-dihydroerythronolide B derivatives and of erythronolide B
  作者：Johann Mulzer、Holger M. Kirstein、Juergen Buschmann、Christian Lehmann、Peter Luger

  DOI：10.1021/ja00003a026

  日期：1991.1

  A convergent total synthesis (22 steps on the longest linear route) of (−)-erythronolide B (5) and two 9-dihydro derivatives (52 and 54) thereof from (R)-2,3-O-isopropylideneglyceraldehyde (20) as the only source of chirality is described. A key step of the synthesis is the regio- and stereocontrolled coupling of the allyl sulfide anion 39 and ketone 26 which can be directed to either α-adduct 40 or

  (-)-erythronolide B (5) 及其两种 9-二氢衍生物（52 和 54）来自 (R)-2,3-O-异亚丙基甘油醛 (20) 的收敛全合成（最长线性路线上的 22 步）作为手性的唯一来源被描述。A key step of the synthesis is the regio- and stereocontrolled coupling of the allyl sulfide anion 39 and ketone 26 which can be directed to either α-adduct 40 or 41 by an appropriate choice of the conditions (Scheme V, table II). 由40和41制备seco酸47和49，根据改进的Yamaguchi程序将其顺利地大环内酯化为50和51。在大环立体控制下进行 50