3-methyl-1-(tri-n-butylstannyl)-3-[(triethylsilyl)oxy]but-1(E)-ene | 132101-35-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 3-methyl-1-(tri-n-butylstannyl)-3-[(triethylsilyl)oxy]but-1(E)-ene
• 英文别名: triethyl-[(E)-2-methyl-4-tributylstannylbut-3-en-2-yl]oxysilane
• CAS: 132101-35-0
• 化学式: C₂₃H₅₀OSiSn
• 分子量: 489.445
• InChiKey: BRFYFJCLWCEBBR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.73
• 重原子数：
  26.0
• 可旋转键数：
  16.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  3-methyl-1-(tri-n-butylstannyl)-3-[(triethylsilyl)oxy]but-1(E)-ene 在 4-二甲氨基吡啶 、 正丁基锂 、 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 54.0h， 生成 (E)-(S)-5-(tert-Butyl-dimethyl-silanyloxy)-6-[(1R,3R,3aR,3bS,6R,6aR,6bR)-3-(tert-butyl-dimethyl-silanyloxy)-3a,6-dimethyl-decahydro-cyclobutadicyclopenten-1-yl]-2-methyl-hepta-3,6-dien-2-ol
  参考文献：
  名称：

  Total synthesis of spatol and other spatane diterpenes

  摘要：

  Total syntheses of three spatane diterpenes stoechospermol (1), 5(R),15(R),18-trihydroxyspata-13,16(E)-diene (2), and (+)-spatol (3) were accomplished from a common intermediate, diol 7. The total synthesis established as R the absolute configuration at the 15-position in 2. Novel stereospecific transformations of 2,3-epoxy-1,4-diols into vicinal diepoxides were demonstrated and exploited for assembling the sensitive allylic diepoxide in the side chain of spatol. This new synthetic method allows the conversion of both 1,2-threo-2,3-trans- and 1,2-erythro-2,3-trans-2,3-epoxy-1,4-diols into vicinal 1,2-cis-2,3-erythro-1,3-diepoxides. Unexpected stability toward hydroxide anion was found for the allylic diepoxide functional array. This observation provides presumptive evidence that acid catalysis is operative in the epoxide cleaving substitution reaction of spatol by the weakly nucleophilic chloride anion that gives chlorohydrin 4. A proclivity for erythro-selective epoxidation of allylic silyl ethers was found. The utility of C-silyl substituents for reversing this stereoselectivity, i.e., favoring threo-selective epoxidation of allylic silyl ethers, was established.

  DOI：

  10.1021/ja00008a044
• 作为产物：
  描述：

  2-methyl-2-<(triethylsilyl)oxy>-3-butyne 、 三正丁基氢锡 以92%的产率得到
  参考文献：
  名称：

  SALOMON, ROBERT G.;BASU, BASUDEB;ROY, SUBHAS;SACHINVALA, NAVZER D., J. AMER. CHEM. SOC., 113,(1991) N, C. 3096-3106

  摘要：

  DOI：

文献信息

• A Short, Efficient Copper-Mediated Synthesis of 1α,25-Dihydroxyvitamin D₂ (1α,25-Dihydroxyergocalciferol) and C-24 Analogs¹^,²
  作者：Mercedes Torneiro、Yagamare Fall、Luis Castedo、Antonio Mouriño

  DOI：10.1021/jo970604u

  日期：1997.9.1

  Two synthetic routes to the nonnatural hormone 1 alpha,25-dihydroxyergocalciferol [2b, 1 alpha,25-(OH)(2)-D-2] and analogs modified at C-24 have been developed both starting from aldehyde 7b. Key steps in route A (eight steps, approximate to 38% overall yield from 7b) are (1) stereoselective addition of (E)-vinyllithium reagent 8c to aldehyde 7b; and (2) S(N)2' anti-displacement of the allylic phosphate of 5e by organocuprates derived from Grignard reagents and CuCN in the presence of LiCl. Key steps in route B (eight steps from 7b, 48% overall yield) are (1) Wittig-Horner type coupling between ketone 22, which bears an allylic phosphate group on the side chain, and the ylide derived from the Lythgoe-Roche phosphine oxide to form the vitamin D triene unit; and (2) efficient S(N)2' anti-displacement of the phosphate group of 23 by the organocuprate derived from MeMgCl, CuCN, and LiCl, without affecting the labile vitamin D triene system, to give, after deprotection, 1 alpha,25-(OH)2-D-2. Route B is particularly attractive as an approach to diverse C-24 vitamin D analogs for biological screening.
• Absolute stereochemistry of aplaminone and neoaplaminone, cytotoxic bromodopamines from a marine mollusc: enantioselective synthesis of debromoneoaplaminone
  作者：Hideo Kigoshi、Yuichi Adachi、Kohji Yoshikawa、Kiyoyuki Yamada

  DOI：10.1016/s0040-4039(00)74687-9

  日期：1992.7

  The absolute stereochemistry of potent cytotoxic bromodopamines, aplaminone and neoaplaminone has been determined by means of enantioselective synthesis of debromoneoaplaminone, a derivative of aplaminone and neoaplaminone.