1-iodo-3-methoxybicyclo<1.1.1>pentane | 136863-37-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-iodo-3-methoxybicyclo<1.1.1>pentane
• 英文别名: 1-methoxy-3-iodobicyclo<1.1.1>pentane；3-iodo-1-methoxybicyclo<1.1.1>pentane；1-iodo-3-methoxybicyclo[1.1.1]pentane
• CAS: 136863-37-1
• 化学式: C₆H₉IO
• 分子量: 224.041
• InChiKey: WNEFWCPKUYOFHZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-iodo-3-methoxybicyclo<1.1.1>pentane 在 偶氮二异丁腈 、 氘代三正丁基锡 作用下， 反应 2.0h， 生成 3-deutero-1-methoxybicyclo<1.1.1>pentane
  参考文献：
  名称：

  Experimental and theoretical study of substituent effects on3J(13C1-1H) coupling constants in 1-X-bicyclo[1.1.1]pentanes

  摘要：

  A series of 23 bridgehead-substituted bicyclo[1,1,1]pentanes were synthesized and the (3)J(C1-H) coupling constants determined from their proton-coupled C-13 NMR spectra. It was found that the values of the couplings are strongly dependent upon the type of substituent present, with powerful effects exerted by the halogens in particular. The IPPP-CLOPPA-INDO theoretical approach, which was employed to provide a measure of the extent of through-bond versus through-space transmission of coupling information, was found to give (3)J(C1-H) values in good agreement with experimental data. Empirical substituent parameter regressions were performed and found to be consistent with the CLOPPA description of the increase in both the through-bond and through-space contributions to the coupling. The substituent parameter regressional analyses also demonstrated that electronegativity effects play a predominant role in determining the magnitude of the couplings, particularly in those substrates in which the substituent is attached to the ring system by a second-row element.

  DOI：

  10.1002/(sici)1099-1395(199603)9:3<168::aid-poc766>3.0.co;2-v
• 作为产物：
  描述：

  甲醇 、 1,3-二碘双环[1.1.1]戊烷 在 sodium methylate 作用下， 反应 96.0h， 以74%的产率得到1-iodo-3-methoxybicyclo<1.1.1>pentane
  参考文献：
  名称：

  Formation and Reactions of Bicyclo[1.1.1]pentyl-1 Cations

  摘要：

  The ionization of l-bicyclo[1.1.1]pentyl halides was shown to initially form the 1,3-bridged bicycle[1.1.1]pentyl-l cation. It appears to be a transition state that leads to the bicyclo[1.1.0]butyl-1-carbinyl cation which can be trapped with azide ion and can be directly observed by NMR in SO2CIF. Although the major products of solvolysis of the halides are 3-methylenecyclobutyl derivatives, the corresponding cation was calculated to have a significantly higher energy than the bicyclobutylcarbinyl ion. Therefore, the products are probably formed by an attack of the nucleophile on the latter ion, accompanied by bond migration. The bridgehead iodide reacts under solvolytic conditions with azide ion to form bicyclo[1.1.0]butyl-l azide as a product. It also reacts with potassium hydroxide to give [1.1.1]propellane, and the same reaction occurs on dissolving in acetonitrile or pyridine. The reaction of 1,3-diiodobicyclo[1.1.1]pentane with ethoxide ion also was found to give [1.1.1]propellane via a nucleophilic attack on one of the iodines. The propellane reacts with methyl hypoiodite to give 3-iodobicyclo[1.1.1]pentyl-l cation, which can react with methanol to give 3-methoxybicyclo[1.1.1]pentyl-l iodide and with azide ion to give 3-iodobicyclo[1.1.1]pentyl-1 azide. These data provide evidence for a discrete 3-iodobicyclo[1.1.1]pentyl-l cation intermediate. The effect of substituents on the rate of solvolysis of bicyclo[1.1.1]pentyl-l iodide was studied. With 3-aryl substituents, a value of rho = -1.7 was found, which is similar to that observed in the solvolysis of 3-arylcyclobutyl tosylates (rho = -1.6). The 3-substituted bicyclopentyl halides usually form the corresponding 3-methylenecyclobutyl cations rather than bicyclo[1.1.0]butyl-1-carbinyl ions, because most substituents will help stabilize the former type of ion.

  DOI：

  10.1021/ja00105a046

文献信息

• Photoinduced Copper‐Catalyzed Coupling of Terminal Alkynes and Alkyl Iodides
  作者：Avijit Hazra、Mitchell T. Lee、Justin F. Chiu、Gojko Lalic

  DOI：10.1002/anie.201801085

  日期：2018.5.4

  We have developed a photoinduced copper‐catalyzed alkylation of terminal alkynes with primary, secondary, or tertiary alkyl iodides as electrophiles. The reaction has a broad substrate scope and can be successfully performed in the presence of ester, nitrile, aryl halide, ketone, sulfonamide, epoxide, alcohol, and amide functional groups. The alkylation is promoted by blue light (λ≈450 nm) and proceeds

  我们已经开发出了以伯，仲或叔烷基碘为亲电试剂的末端炔烃的光诱导铜催化烷基化反应。该反应具有广泛的底物范围，并且可以在酯，腈，卤代芳基，酮，磺酰胺，环氧化物，醇和酰胺官能团的存在下成功进行。该烷基化是由蓝色光促进（λ ≈450nm）与在没有任何附加的金属催化剂的室温下进行。联吡啶配体的使用对于反应的成功至关重要，而且可以防止光诱导的铜催化原料的聚合。
• Nucleophilic substitution in 1-substituted 3-iodobicyclo[1.1.1]pentanes. A new synthetic route to functionalized bicyclo[1.1.1]pentane derivatives
  作者：James L. Adcock、Andrei A. Gakh

  DOI：10.1021/jo00049a030

  日期：1992.11

  Nucleophilic substitution of the iodine in 1-substituted 3-iodobicyclo[1.1.1]pentanes [R = I (1), CF3 (2)] was investigated. The results of the reaction are strongly dependent on the nature of the nucleophile and the substituent. Whereas the trifluoromethyl derivative 2 is found to be inert in the reactions and gave substitution products only with organolithium reagents, the 1,3-diiodide 1 is much more reactive and affords normal substitution products with nitrogen bases and MeONa but gives [1.1.1]propellane with Grignard and organolithium reagents and with triaryl(alkyl)phosphines. Other synthesized 3-iodobicyclo[1.1.1]pentanes did not give substitution products. A general scheme for the transformations of 1 is also proposed.
• Synthesis of Some Bridgehead-Bridgehead-Disubstituted Bicyclo[1.1.1]pentanes
  作者：Ernest W. Della、Dennis K. Taylor

  DOI：10.1021/jo00090a015

  日期：1994.6

  The synthesis of a wide variety of 1,3-disubstituted bicyclo[1.1.1]pentanes is described, with particular emphasis on the generation of a series of S-X-substituted bicyclo[1.1.1]pentyl bromides required for solvolytic studies. Functional group manipulation at the bridgehead was readily accomplished in the majority of cases by radical processes in some instances, transformations were effected via carbanionic-type intermediates.
• Experimental and theoretical study of substituent effects on3J(13C1-1H) coupling constants in 1-X-bicyclo[1.1.1]pentanes
  作者：Ernest W. Della、Ian J. Lochert、N�lida M. Peruchena、Gustavo A. Aucar、Rub�n H. Contreras

  DOI：10.1002/(sici)1099-1395(199603)9:3<168::aid-poc766>3.0.co;2-v

  日期：1996.3

  A series of 23 bridgehead-substituted bicyclo[1,1,1]pentanes were synthesized and the (3)J(C1-H) coupling constants determined from their proton-coupled C-13 NMR spectra. It was found that the values of the couplings are strongly dependent upon the type of substituent present, with powerful effects exerted by the halogens in particular. The IPPP-CLOPPA-INDO theoretical approach, which was employed to provide a measure of the extent of through-bond versus through-space transmission of coupling information, was found to give (3)J(C1-H) values in good agreement with experimental data. Empirical substituent parameter regressions were performed and found to be consistent with the CLOPPA description of the increase in both the through-bond and through-space contributions to the coupling. The substituent parameter regressional analyses also demonstrated that electronegativity effects play a predominant role in determining the magnitude of the couplings, particularly in those substrates in which the substituent is attached to the ring system by a second-row element.
• Formation and Reactions of Bicyclo[1.1.1]pentyl-1 Cations
  作者：Kenneth B. Wiberg、Neil McMurdie

  DOI：10.1021/ja00105a046

  日期：1994.12

  The ionization of l-bicyclo[1.1.1]pentyl halides was shown to initially form the 1,3-bridged bicycle[1.1.1]pentyl-l cation. It appears to be a transition state that leads to the bicyclo[1.1.0]butyl-1-carbinyl cation which can be trapped with azide ion and can be directly observed by NMR in SO2CIF. Although the major products of solvolysis of the halides are 3-methylenecyclobutyl derivatives, the corresponding cation was calculated to have a significantly higher energy than the bicyclobutylcarbinyl ion. Therefore, the products are probably formed by an attack of the nucleophile on the latter ion, accompanied by bond migration. The bridgehead iodide reacts under solvolytic conditions with azide ion to form bicyclo[1.1.0]butyl-l azide as a product. It also reacts with potassium hydroxide to give [1.1.1]propellane, and the same reaction occurs on dissolving in acetonitrile or pyridine. The reaction of 1,3-diiodobicyclo[1.1.1]pentane with ethoxide ion also was found to give [1.1.1]propellane via a nucleophilic attack on one of the iodines. The propellane reacts with methyl hypoiodite to give 3-iodobicyclo[1.1.1]pentyl-l cation, which can react with methanol to give 3-methoxybicyclo[1.1.1]pentyl-l iodide and with azide ion to give 3-iodobicyclo[1.1.1]pentyl-1 azide. These data provide evidence for a discrete 3-iodobicyclo[1.1.1]pentyl-l cation intermediate. The effect of substituents on the rate of solvolysis of bicyclo[1.1.1]pentyl-l iodide was studied. With 3-aryl substituents, a value of rho = -1.7 was found, which is similar to that observed in the solvolysis of 3-arylcyclobutyl tosylates (rho = -1.6). The 3-substituted bicyclopentyl halides usually form the corresponding 3-methylenecyclobutyl cations rather than bicyclo[1.1.0]butyl-1-carbinyl ions, because most substituents will help stabilize the former type of ion.