(1R*,7S*)-Bicyclo[5.3.1]undecan-9-one | 77188-49-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R*,7S*)-Bicyclo[5.3.1]undecan-9-one
• 英文别名: (1S,7R)-bicyclo[5.3.1]undecan-9-one
• CAS: 77188-49-9
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: MKWKLEAIFLWBEU-AOOOYVTPSA-N

物化性质

• 沸点：
  70-75 °C(Press: 0.5 Torr)
• 密度：
  0.962±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1R*,7S*)-Bicyclo[5.3.1]undecan-9-one 在 Amberlyst 15 、 4 A molecular sieve 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 正己烷 为溶剂， 反应 47.83h， 生成
  参考文献：
  名称：

  Constructing Conformationally Constrained Macrobicyclic Musks

  摘要：

  To investigate the structure odor correlation of musks,(12R)-12-methyl-13-tridecanotide (1), a macrocyclic musk, and 13-tridecanolide. its non-musky demethyl analogue. were conformationally constrained by introduction of methylene bridges between C-3 and C-8 or C-9. These [7.5.1]- and [8.4.1]macrobicycles were synthesized starting from bicyclo[5.3.1]undec-8-en-9-one (3) and bicyclo[4.3.1]dec-7-en-8-one (8), respectively, by a sequence consisting of catalytic hydrogenation. a-alkylation with a TBS-protected (tert-butyldimethylsilyl) hydroxy halide., acid-catalyzed cyclization, oxidative cleavage of the formed enol ether double bond, and subsequent reduction of the carbonyl group via its tosylhydrazone. The compound (1R,6R,9R)-(+)-6-methyl-4-oxa-bicyclo[7.5.1]pentadecan-3-one (22) was found to possess the most pronounced musk odor, and this was rationalized by a superposition analysis with the polycyclic aromatic musk odorant (4S,7R)-Galaxolide (2). In its (1S,6R,9S)-(+)stereoisomer-23 as well as in (1S,6R, 10R)-(+)-6-methyl-4-oxabicyclo-[8.4.1]pentadecan-3-one (18) the (6R)-methyl group seems to hinder the interaction with the musk receptor, while the demethyl compounds 7 and 12 showed only very faint odors.

  DOI：

  10.1002/1521-3765(20010803)7:15<3254::aid-chem3254>3.0.co;2-#
• 作为产物：
  描述：

  Bicyclo [5.3.1]undec-10-en-9-one 在 10percent Pd/C 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 7.0h， 以70%的产率得到(1R*,7S*)-Bicyclo[5.3.1]undecan-9-one
  参考文献：
  名称：

  Constructing Conformationally Constrained Macrobicyclic Musks

  摘要：

  To investigate the structure odor correlation of musks,(12R)-12-methyl-13-tridecanotide (1), a macrocyclic musk, and 13-tridecanolide. its non-musky demethyl analogue. were conformationally constrained by introduction of methylene bridges between C-3 and C-8 or C-9. These [7.5.1]- and [8.4.1]macrobicycles were synthesized starting from bicyclo[5.3.1]undec-8-en-9-one (3) and bicyclo[4.3.1]dec-7-en-8-one (8), respectively, by a sequence consisting of catalytic hydrogenation. a-alkylation with a TBS-protected (tert-butyldimethylsilyl) hydroxy halide., acid-catalyzed cyclization, oxidative cleavage of the formed enol ether double bond, and subsequent reduction of the carbonyl group via its tosylhydrazone. The compound (1R,6R,9R)-(+)-6-methyl-4-oxa-bicyclo[7.5.1]pentadecan-3-one (22) was found to possess the most pronounced musk odor, and this was rationalized by a superposition analysis with the polycyclic aromatic musk odorant (4S,7R)-Galaxolide (2). In its (1S,6R,9S)-(+)stereoisomer-23 as well as in (1S,6R, 10R)-(+)-6-methyl-4-oxabicyclo-[8.4.1]pentadecan-3-one (18) the (6R)-methyl group seems to hinder the interaction with the musk receptor, while the demethyl compounds 7 and 12 showed only very faint odors.

  DOI：

  10.1002/1521-3765(20010803)7:15<3254::aid-chem3254>3.0.co;2-#

文献信息

• Structural analysis of cis-[n.3.1]bicyclic ketones by x-ray crystallography. Impact of the observed conformational crossover by .pi.-facially diastereoselective nucleophilic additions to this class of ketones and on the stereochemical course of electrophilic reactions involving their methylene analogs
  作者：Leo A. Paquette、Ted L. Underiner、Judith C. Gallucci

  DOI：10.1021/jo00027a018

  日期：1992.1

  X-ray crystallographic studies clearly show that cis-[n.3.1]bicyclic ketones 1 having n equal to 7 or less are conformationally predisposed such that the rigid chair cyclohexanone ring projects the polymethylene chain diaxially. In contrast, an increase in belt size to n = 9 is adequate to allow adoption of diequatorial geometry without evidence for dynamic chair-chair interconversion. These divergent ground-state characteristics are believed to persist in the methylene derivatives 2. In order to evaluate the impact of this stereochemical crossover on the facial stereoselectivity of nucleophilic attack on 1 and electrophilic capture by 2, the following reactions were examined: hydride and dissolving metal reduction, organometallic additions, condensation with dimethyloxosulfonium methylide, epoxidation, osmylation, oxymercuration, and cycloadditions involving chlorosulfonyl isocyanate and dichloroketene. The presence of an axially oriented loop strongly curtails otherwise favored axial approach by these reagents. With these systems, a strong preference for less hindered equatorial approach is observed. Although the (CH2)9 series is subject to near-identical inductive contributions from the polymethylene belt, the overwhelming diequatorial bias of this belt does not introduce a comparable steric bias and a general (although not exclusive) preference for axial attack is noted. These substitution effects are compared to those of the 4-tert-butylcyclohexyl analogues.
• Asymmetric functionalization of conformationally distinctive Cs-symmetric cis-[n.3.1] bicyclic ketones. Definition of the absolute course of enantio- and diastereodifferentiation
  作者：Theodore L. Underiner、Leo A. Paquette

  DOI：10.1021/jo00046a028

  日期：1992.9

  The four C(s)-symmetric cis[n.3.1] bicyclic ketones where n = 3, 5, 7, and 9 were acetalized with (R,R)-2,4-pentanediol, and the resulting derivatives were cleaved with triisobutylaluminum (TRIBAL). The first three examples, all of which have their polymethylene chain rigidly fixed in a diaxial orientation, undergo ring opening with very high diastereoselectivity to give 5. In the fourth case (n = 9), the chain is sufficiently long to be attached in a diequatorial manner. The response of 4d to TRIBAL is to deliver a 1:1 mixture of 11 and 12. The stereochemical course of epoxidation and cyclopropanation reactions of these enol ethers has been assessed. Where 5 and 11 are concerned, these functionalization reactions are 100% pi-facially selective. Only 12 is the exception. Also examined in this study was the enantioselective deprotonation of the same ketones with the enantiomerically pure lithium amide base 27. The resulting enolates were trapped as their silyl enol ethers and transformed directly into optically active alpha-hydroxy ketones and alpha,beta-unsaturated enones by epoxidation and selenenylation-oxidative elimination, respectively. The sense of the observed enantioselectivity was the same irrespective of the diaxial or diequatorial disposition of the (CH2)n loop. However, the asymmetry induced by this means was consistently opposite to that realized by TRIBAL-promoted acetal cleavage. When these complementary processes are compared at the alpha-hydroxy ketone stage, the acetal cleavage-epoxidation option was invariably 100% enantioselective; greater variability in optical purity was seen via the deprotonation-silylation-epoxidation option. The possible mechanistic basis of these observations is explored.
• Constructing Conformationally Constrained Macrobicyclic Musks
  作者：Philip Kraft、Riccardo Cadalbert

  DOI：10.1002/1521-3765(20010803)7:15<3254::aid-chem3254>3.0.co;2-#

  日期：2001.8.3

  To investigate the structure odor correlation of musks,(12R)-12-methyl-13-tridecanotide (1), a macrocyclic musk, and 13-tridecanolide. its non-musky demethyl analogue. were conformationally constrained by introduction of methylene bridges between C-3 and C-8 or C-9. These [7.5.1]- and [8.4.1]macrobicycles were synthesized starting from bicyclo[5.3.1]undec-8-en-9-one (3) and bicyclo[4.3.1]dec-7-en-8-one (8), respectively, by a sequence consisting of catalytic hydrogenation. a-alkylation with a TBS-protected (tert-butyldimethylsilyl) hydroxy halide., acid-catalyzed cyclization, oxidative cleavage of the formed enol ether double bond, and subsequent reduction of the carbonyl group via its tosylhydrazone. The compound (1R,6R,9R)-(+)-6-methyl-4-oxa-bicyclo[7.5.1]pentadecan-3-one (22) was found to possess the most pronounced musk odor, and this was rationalized by a superposition analysis with the polycyclic aromatic musk odorant (4S,7R)-Galaxolide (2). In its (1S,6R,9S)-(+)stereoisomer-23 as well as in (1S,6R, 10R)-(+)-6-methyl-4-oxabicyclo-[8.4.1]pentadecan-3-one (18) the (6R)-methyl group seems to hinder the interaction with the musk receptor, while the demethyl compounds 7 and 12 showed only very faint odors.