2,2-dimethyl-4-(2-furyl)hydroxymethyl-1,3-dioxolane | 80541-31-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2-dimethyl-4-(2-furyl)hydroxymethyl-1,3-dioxolane
• 英文别名: (R)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-(furan-2-yl)methanol
• CAS: 80541-31-7
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: LSFNLMRNUXQZKU-BDAKNGLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  51.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,2-dimethyl-4-(2-furyl)hydroxymethyl-1,3-dioxolane 在 四丁基氟化铵 、 叔丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 30.0h， 生成 *,R^*)>-2,2-Dimethyl-α-<5-<(phenylmethoxy)methyl>-2-furanyl>-1,3-dioxolane-4-methanol
  参考文献：
  名称：

  The furan approach to oxygenated natural products. Total synthesis of (+)-KDO

  摘要：

  A de novo asymmetric synthesis of the higher monosaccharide 3-deoxy-D-manno-2-octulosonic acid, (+)-KDO (1), was completed in 12 steps starting from furan and isopropylidene-D-glyceraldehyde. The synthesis commenced with the conversion of furan (4) into the protected furfuryl carbinol 5 by the highly stereoselective addition of 2-lithiofuran to isopropylidene-D-glyceraldehyde and subsequent trapping of the intermediate alkoxide. Metalation of 5 followed by alkylation with benzyl chloromethyl ether and hydroxyl deprotection then provided 9 in a single operation. The key transformation of the synthesis entailed sequential oxidative processing of 9 with t-BuOOH in the presence of a catalytic amount of VO(acac)2 and O-methylation of the intermediate hemiacetal moiety to furnish the alpha-methyl glycoside 12 as the major product. Stereoselective 1,2-reduction of 12 using K-Selectride (Aldrich) gave the allylic alcohol 15, which was elaborated to 20 by electrophile-induced cyclization of the allylic carbamate 19. Refunctionalization of 20 proceeded in a straightforward fashion by a process involving reductive removal of iodide at C(3) and the benzyl protecting group at C(1) to furnish 23. Oxidation of the intermediate primary alcohol moiety at C(1) of 23 and deprotection of the remaining hydroxyl functions delivered (+)-KDO (1).

  DOI：

  10.1021/jo00023a028
• 作为产物：
  描述：

  (R)-2,3-isopropylidenedioxy-1-(2-furyl)-1-propanone 生成 2,2-dimethyl-4-(2-furyl)hydroxymethyl-1,3-dioxolane
  参考文献：
  名称：

  CHIKASHITA, HIDENORI;NIKAYA, TOSHIKI;UEMURA, HIROMITSU;ITOH, KAZUYOSHI, BULL. CHEM. SOC. JAP., 62,(1989) N, C. 2121-2123

  摘要：

  DOI：

文献信息

• THE STEREOSELECTIVE SYNTHESIS OF D-RIBULOSE
  作者：Keisuke Suzuki、Yoichi Yuki、Teruaki Mukaiyama

  DOI：10.1246/cl.1981.1529

  日期：1981.11.5

  In the presence of zinc halide, 2-furyllithium reacts with 2,3-O-isopropylidene-d-glyceraldehyde in a highly stereoselective manner to give the chiral and stereo-defined alcohol, 2,2-dimethyl-4-(2-furyl)hydroxymethyl-1,3-dioxolane, which is further elaborated to afford d-ribulose in three steps.

  在卤化锌存在下，2-呋喃锂与 2,3-O-isopropylidene-d-glyceraldehyde 以高度立体选择性的方式发生反应，生成手性和立体定义的 2,2-二甲基-4-(2-呋喃基)羟甲基-1,3-二氧戊环。
• Stereocontrolled syntheses of novel styryl lactones, (+)-goniodiol, (+)-goniotriol, (+)-8-acetylgoniotriol, (+)-goniofufurone, (+)-9-deoxygoniopypyrone, (+)-goniopypyrone, and (+)-altholactone from common intermediates and cytotoxicity of their congeners
  作者：Masayoshi Tsubuki、Kazuo Kanai、Hiromasa Nagase、Toshio Honda

  DOI：10.1016/s0040-4020(99)00023-x

  日期：1999.2

  Concise syntheses of (+)-goniodiol, (+)-goniotriol, (+)-8-acetylgoniotriol, (+)-goniofufurone, (+)-9-deoxygoniopypyrone, (+)-goniopypyrone, and (+)-altholactone and their congeners from chiral lactonic aldehydes 27 and 36 as common intermediates are described. The key features in the syntheses are based on the in situ generation of unstable aldehydes 27 and 36 followed by their chemoselective reaction

  简捷合成（+）-goniodiol，（+）-goniotriol，（+）-8-乙酰基goniotriol，（+）-goniofufurone，（+）-9-脱氧goniopypyrone，（+）-goniopypyrone和（+）-邻甲内酯描述了它们来自手性内酯醛27和36的同类物，作为常见的中间体。合成中的关键特征是基于原位生成不稳定的醛27和36，然后它们与三异丙氧基苯基钛发生化学选择性反应，从而在C-8位提供非对映异构体28、29和37、38。检查了苯乙烯基内酯同源物对P388鼠白血病细胞的细胞毒性。
• Stereoselective total synthesis of bengamide E from glyceraldehyde acetonide and a nonracemic .gamma.-alkoxy allylic stannane
  作者：James A. Marshall、George P. Luke

  DOI：10.1021/jo00075a017

  日期：1993.11

  The synthesis of bengamide E (30) was achieved starting from the furan adduct 1 of (R)-glyceraldehyde acetonide. The key step entailed MgBr2-promoted addition of the (S)-gamma-alkoxy allylic stannane (S)-25 to the aldehyde 8 obtained from the oxidation product of furan 1 after protection as the methyl ether. The adduct of stannane (S)-25 and aldehyde 8, a 1:1 mixture of hydroxy ester 27 and lactone 28 was converted to bengamide E by aminolysis with (S)-2-aminocaprolactam and subsequent debenzylation with Li in NH3.
• Exciton chirality method for establishing absolute configuration of 2-furylcarbinols
  作者：Jacek Gawronski、Dariusz Radocki、Janusz Jurczak、Zbigniew Pakulski、Jerzy Raczko、Jan Ramza、Aleksander Zamojski

  DOI：10.1021/jo00290a061

  日期：1990.2
• Diastereoselective addition (η2-alkyne)Ti(O-i-Pr)2 complexes to 2,3-O-isopropylideneglyceraldehyde
  作者：Koki Yamashita、Hirokazu Urabe、Fumie Sato

  DOI：10.1016/s0040-4039(97)00990-8

  日期：1997.6

  The title alkyne-titanium complexes, prepared from propargyl ethers, Ti(O-i-Pr)(4), and i-PrMgCl, reacted with 2,3-O-isopropylideneglyceraldehyde in good to excellent diastereoselectivities of up to 94:6 to afford the anti-adducts, which are useful precursor for the preparation of optically active polyhydroxy compounds. (C) 1997 Elsevier Science Ltd.