(4-methylpent-3-en-1-yl)triphenylphosphonium bromide | 27312-92-1

• 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: (4-methylpent-3-en-1-yl)triphenylphosphonium bromide
• 英文别名: 4-methyl-3-pentenyltriphenylphosphonium bromide；4-Methyl-3-pentyltriphenylphosphonium bromide；(4-methyl-3-pentenyl)triphenylphosphonium bromide；4-Methyl-3-pentenyltriphenylphosphoniumbromid；Phosphonium, (4-methyl-3-pentenyl)triphenyl-, bromide；4-methylpent-3-enyl(triphenyl)phosphanium;bromide
• CAS: 27312-92-1
• 化学式: Br*C₂₄H₂₆P
• 分子量: 425.348
• InChiKey: UTNDSPMMHRRXQW-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.34
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (4-methylpent-3-en-1-yl)triphenylphosphonium bromide 在 titanium(IV) isopropylate 、 2,3,5-三甲基吡啶 、 叔丁基过氧化氢 、 草酰氯 、 ammonium chloride 、 4-甲基苯磺酸吡啶 、 双(三甲基硅烷基)氨基钾 、 D-(-)-酒石酸二异丙酯 、 二甲基亚砜 、 三乙胺 、 三氟乙酸 、 十二硫醇 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 乙醇 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 47.47h， 生成
  参考文献：
  名称：

  Total Syntheses of the Cytotoxic Marine Natural Product, Aplysiapyranoid C¹

  摘要：

  The first total syntheses of the cytotoxic marine natural product, aplysiapyranoid C, 1c, are reported. The Wittig reaction of 4-methyl-3-pentenyltriphenylphosphorane with the THP ether of hydroxyacetone gave in 88% yield the Z-alkene 4 which was hydrolyzed to the alcohol 5 in 72% yield. Sharpless asymmetric epoxidation of 5 afforded the epoxy alcohol 6 in 91% yield and 81% ee, Opening of the epoxide of 6 with ammonium chloride in DMSO gave in 76% yield the chloro diol 7 which was converted to the primary TBS ether 8 in 95% yield. Opening of the epoxy alcohol 6 with HCl and Ti(OiPr)(4) afforded the desired chloro diol 7 as the minor product along with the rearranged chloromethyl diol 9. This compound is presumably formed by opening of the protonated epoxide to give a butenyl cation which rearranges to the cyclopropylcarbinyl cation and is then trapped by chloride ion at the unsubstituted cyclopropyl carbon, regenerating the alkene. Cyclization of the TBS ether 8 with tetrabromocyclohexadienone (TBCO) afforded a mixture of all four possible cyclization products, the desired tetrahydropyrans 11a,b and the tetrahydrofurans 12a,b with the former being isolated in 70% yield. Hydrolysis of the TBS ether afforded the primary alcohols from which the desired isomer, 13, could be isolated (24% overall from 8), Swern oxidation furnished the aldehyde 14 which was subjected to the Takai chlorovinylation to give a mixture of aplysiapyranoid C Ic and the reduced product, dechloroaplysiapyranoid C 15. This dechlorination under these conditions is quite unusual. A second synthesis of aplysiapyranoid C avoided this problem. Selective protection of the more hindered tertiary alcohol of the chloro diol 7 afforded the primary alcohol 16 in which the tertiary alcohol was protected as the triethylsilyl ether. Swern oxidation, Takai reaction, and desilylation gave the dichloro alkenol 17 in 52% overall yield. In this case, only a small amount of the corresponding dechlorinated product was obtained. Final cyclization of 17 with TBCO afforded aplysiapyranoid C Ic as the major product in an isolated yield of 43%. Thus we have completed two total syntheses of aplysiapyranoid C Ic from the simple bromide 2 in eight or nine steps and good overall yield.

  DOI：

  10.1021/jo972228j
• 作为产物：
  描述：

  5-溴-2-甲基-2-戊烯 、 三苯基膦 在 氮气 、 乙醚 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以to afford 905 mg of (4-methyl-3-pentenyl)triphenylphosphonium bromide的产率得到(4-methylpent-3-en-1-yl)triphenylphosphonium bromide
  参考文献：
  名称：

  7-oxabicyclo(2.2.1)heptane compounds useful in the treatment of

  摘要：

  公开了具有通式 ##STR1## 的7-氧杂双环[2.2.1]庚烷类似物，其中R.sub.1是较低的烷基，烯基，取代烯基或炔基; R.sub.2是较低的烷基，烯基或炔基; A是--CH.sub.2--CH.dbd.CH--或单键; X是--CH.sub.2，--CH(CH.sub.3)或--C(CH.sub.3).sub.2; n是从0到9的整数，但当A是单键时，n是从1到9的整数; 包括所有立体异构体。已发现这些新化合物是花生四烯酸环氧化酶的抑制剂，因此可用作抗炎，退热和镇痛剂。

  公开号：

  US04707494A1

文献信息

• Simple Synthesis of Mite Pheromone β-Acaridial and Its Analogs in the Secretion of<i>Caloglyphus polyphyllae</i>(Acari: Acaridae)
  作者：Nobuhiro SHIMIZU、Naoki MORI、Yasumasa KUWAHARA

  DOI：10.1271/bbb.67.1732

  日期：2003.1

  A simple synthesis of beta-acaridial [(E)-1], the active principle of the sex, alarm and aggregation pheromone among astigmatid mites, was achieved in 5 steps from 1,2,4-butanetriol 2 in a 19% overall yield. Its analog, beta-acariolal 8, was also prepared in a 63% yield by oxidation of the intermediate, beta-acaridiol [(E)-7], with pyridinium dichromate (PDC). This synthetic route also gave beta-(Z)-acaridiol

  从1,2,4-丁三醇2分5步就可以轻松合成β-芳烃[（E）-1]，这是散光螨中性，警报和聚集信息素的有效成分，总产率为19％ 。还通过用重铬酸吡啶鎓（PDC）氧化中间体β-ac二醇[[E] -7]，以63％的产率制备了其类似物β-ari醛8。通过在Wittig反应中使用Z-选择性碱，该合成途径还得到了β-（Z）-ac二醇[（Z）-7]。将（Z）-7氧化，得到新的单萜β-（Z）-芳烃[（Z）-1]，该化合物被作为多叶草的分泌物中的痕量成分与8一起检测到。
• Synthetic Studies on the Natural Product Myrsinoic Acid F Reveal Biologically Active Analogues
  作者：Jiri Mikusek、Jeremy Nugent、Jas S. Ward、Brett D. Schwartz、Alison D. Findlay、Jonathan S. Foot、Martin G. Banwell

  DOI：10.1021/acs.orglett.8b01558

  日期：2018.7.6

  The synthesis of the structure, 1, assigned to the anti-inflammatory natural product myrsinoic acid F is reported together with a means for preparing its Z-isomer 21. While neither of these compounds corresponds to the natural product, both of them are anti-inflammatory agents (as determined using a mouse ear edema assay) with congener 1 being notably more potent than the widely prescribed NSAID indometacin

  报告了结构1的合成，该结构被分配给抗炎天然产物肉豆蔻酸F以及制备其Z异构体21的方法。尽管这两种化合物都不是天然产物，但它们都是抗炎药（如使用鼠耳水肿测定法测定），同源物1的功效明显优于广泛使用的NSAID吲哚美辛。
• 7-oxabicyclo(2.2.1)heptane compounds useful in the treatment of
  申请人：E. R. Squibb & Sons, Inc.

  公开号：US04707494A1

  公开（公告）日：1987-11-17

  7-Oxabicyclo(2.2.1)heptane analogs are disclosed having the general formula ##STR1## wherein R.sub.1 is lower alkyl, alkenyl, substituted alkenyl or alkynyl; R.sub.2 is lower alkyl, alkenyl or alkynyl; A is --CH.sub.2 --CH.dbd.CH-- or a single bond; X is --CH.sub.2, --CH(CH.sub.3) or --C(CH.sub.3).sub.2 ; n is an integer from 0 to 9, with the proviso that when A is a single bond, n is an integer from 1 to 9; including all stereoisomers. These new compounds have been found to be inhibitors of arachidonic acid cyclooxygenase and are therefore useful as antiinflammatory antipyretic and analgesic agents.

  公开了具有通式 ##STR1## 的7-氧杂双环[2.2.1]庚烷类似物，其中R.sub.1是较低的烷基，烯基，取代烯基或炔基; R.sub.2是较低的烷基，烯基或炔基; A是--CH.sub.2--CH.dbd.CH--或单键; X是--CH.sub.2，--CH(CH.sub.3)或--C(CH.sub.3).sub.2; n是从0到9的整数，但当A是单键时，n是从1到9的整数; 包括所有立体异构体。已发现这些新化合物是花生四烯酸环氧化酶的抑制剂，因此可用作抗炎，退热和镇痛剂。
• Electronic Tuning of Fischer Carbene Complexes in the Preparation of Bicyclo[3.1.1]heptanones as Taxane A-ring Synthons
  作者：Weiqin Jiang、Michael J Fuertes、William D Wulff

  DOI：10.1016/s0040-4020(99)01101-1

  日期：2000.4

  A synthetic route to taxol and other Taxus diterpenes is described which employs as a key step the reaction between a Fischer carbene complex and a 1,6 enyne to construct 1-substituted-7,7-dimethyl-2-methylenebicyclo[3.1.1] heptan-6-ones. It was found that the reaction between complex 2 and 7-methyl-3-methylene-6-octen-1-yne (dienyne 30) yielded a mixture of bicyclo[3.1.1]heptanone 35 and cyclobutenone 36, the latter possibly arising from the migration of the chromium fragment from an electron-rich alkene to a less electron-rich alkene in the vinyl carbene complex intermediate (i.e. 40-42). On this basis, it was expected that bicycloheptanone yields would increase with increasing electron deficiency in the intermediate 40 since this should lead to more competitive CO insertion. This was observed with a series of electronically modified carbene complexes (45 and 48a-d). The more electron deficient complexes gave good yields of bicycloheptanones, thus providing an efficient means for preparing taxane A-ring synthons. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Claisen rearrangement of 3,4-dihydro-2H-pyranylethylenes. Synthesis of cyclohexenes
  作者：George Buechi、J. E. Powell

  DOI：10.1021/ja00713a034

  日期：1970.5