2-chloroallyl mesylate | 1404492-25-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 2-chloroallyl mesylate
• 英文别名: 2-chloroallyl methanesulfonate；2-Chloroprop-2-enyl methanesulfonate；2-chloroprop-2-enyl methanesulfonate
• CAS: 1404492-25-6
• 化学式: C₄H₇ClO₃S
• 分子量: 170.617
• InChiKey: GUQDMJHXAZZELE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-methyl-2,2-dimethyl-5-triethylsilyloxy-1,3-diox-4-ene 、 2-chloroallyl mesylate 在 (S)-(CF₃)₃-t-BuPHOX 、 Pd(dmdba)₂ 、 四丁基二氟三苯硅酸铵 作用下， 以 甲苯 为溶剂， 生成 (S)-4-(2-chloroallyl)-2,2,4-trimethyl-1,3-dioxan-5-one
  参考文献：
  名称：

  Model Studies To Access the [6,7,5,5]-Core of Ineleganolide Using Tandem Translactonization–Cope or Cyclopropanation–Cope Rearrangements as Key Steps

  摘要：

  Recently, we reported a convergent cyclopropanation-Cope approach to the core of ineleganolide, which was the first disclosed synthesis of the core of the norditerpene natural product ineleganolide. In this complementary work, a model system for the core of ineleganolide has been prepared through a series of tandem cyclo-propanation-Cope and translactonization-Cope rearrangements. Work with this model system has enriched our understanding of the cyclopropanation-Cope rearrangement sequence. Additionally, research into this model system has driven the development of tandem translactonization-Cope rearrangements.

  DOI：

  10.1021/acs.joc.7b02030
• 作为产物：
  描述：

  2-氯-2-丙烯-1-醇 、 甲基磺酰氯 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以95%的产率得到2-chloroallyl mesylate
  参考文献：
  名称：

  Enantioselective Synthesis of a Hydroxymethyl-cis-1,3-cyclopentenediol Building Block

  摘要：

  A brief, enantioselective synthesis of a hydroxymethyl-cis-1,3-cyclopentenediol building block is presented. This scaffold allows access to the cis-1,3-cyclopentanediol fragments found in a variety of biologically active natural and non-natural products. This rapid and efficient synthesis is highlighted by the utilization of the palladium-catalyzed enantioselective allylic alkylation of dioxanone substrates to prepare tertiary alcohols.

  DOI：

  10.1021/ol3027297

文献信息

• Traversing Steric Limitations by Cooperative Lewis Base/Palladium Catalysis: An Enantioselective Synthesis of α‐Branched Esters Using 2‐Substituted Allyl Electrophiles
  作者：Kevin J. Schwarz、Colin M. Pearson、Gabriel A. Cintron‐Rosado、Peng Liu、Thomas N. Snaddon

  DOI：10.1002/anie.201803277

  日期：2018.6.25

  Cooperative catalysis enables the direct enantioselective α‐allylation of linear prochiral esters with 2‐substituted allyl electrophiles. Critical to the successful development of the method was the recognition that metal‐centered reactivity and the source of enantiocontrol are independent. This feature is unique to simultaneous catalysis events and permits logical tuning of the supporting ligands

  协同催化使线性前手性酯与2-取代的烯丙基亲电试剂直接对映选择性α-烯丙基化。该方法成功开发的关键是认识到以金属为中心的反应性和对映体控制的来源是独立的。该特征对于同时发生的催化事件是独特的，并允许在不影响对映选择性的情况下对支持配体进行逻辑调节。
• An enantioselective synthesis of α-alkylated pyrroles <i>via</i> cooperative isothiourea/palladium catalysis
  作者：W. Rush Scaggs、Toya D. Scaggs、Thomas N. Snaddon

  DOI：10.1039/c8ob02600a

  日期：——

  Herein we describe the direct enantioselective Lewis base/Pd catalysed α-allylation of pyrrole acetic acid esters. This provides high isolated yields of highly enantioenriched products and exhibits broad reaction scope with respect to both reaction partners. The products can be readily elaborated in a manner which points towards potential applications in target directed synthesis.

  在此，我们描述了吡咯乙酸酯的直接对映选择性路易斯碱/Pd 催化的 α-烯丙基化。这提供了高度对映体富集的产物的高分离产率，并且对于两种反应伙伴表现出广泛的反应范围。该产品可以很容易地以一种指向目标定向合成的潜在应用的方式进行阐述。
• Development of a Unified Enantioselective, Convergent Synthetic Approach Toward the Furanobutenolide-Derived Polycyclic Norcembranoid Diterpenes: Asymmetric Formation of the Polycyclic Norditerpenoid Carbocyclic Core by Tandem Annulation Cascade
  作者：Robert A. Craig、Russell C. Smith、Jennifer L. Roizen、Amanda C. Jones、Scott C. Virgil、Brian M. Stoltz

  DOI：10.1021/acs.joc.7b02825

  日期：2018.4.6

  enantioselective and diastereoselective approach toward the synthesis of the tetracyclic scaffold of the furanobutenolide-derived polycyclic norditerpenoids is described. Focusing on synthetic efforts toward ineleganolide, the synthetic approach utilizes a palladium-catalyzed enantioselective allylic alkylation for the construction of the requisite chiral tertiary ether. A diastereoselective cyclopropanation–Cope

  描述了对呋喃丁烯内酯衍生的多环降二萜类化合物的四环支架的合成的对映选择性和非对映选择性方法。着眼于针对烯丙基醇的合成努力，合成方法利用钯催化的对映选择性烯丙基烷基化反应来构建所需的手性叔醚。非对映选择性的环丙烷化-Cope重排级联使ineleganolide [6,7,5,5]-四环支架的会聚组装成为可能。讨论了用于此关键串联环化工艺的底物的研究，以及[6,7,5,5]-四环支架的合成操作以及[6,7,5,5]-四环支架的伊莱诺醇内酯向内酯的相互转化的尝试。 ca虫内酯A及其天然异构体的[7,6,5,5]核异构体。
• Enantioselective, convergent synthesis of the ineleganolide core by a tandem annulation cascade
  作者：Robert A. Craig, II、Jennifer L. Roizen、Russell C. Smith、Amanda C. Jones、Scott C. Virgil、Brian M. Stoltz

  DOI：10.1039/c6sc03347d

  日期：——

  assembly of the ineleganolide [6,7,5,5]-tetracyclic scaffold by a diastereoselective cyclopropanation–Cope rearrangement cascade under unusually mild conditions. Computational evaluation of ground state energies of late-stage synthetic intermediates was used to guide synthetic development and aid in the investigation of the conformational rigidity of these highly constrained and compact polycyclic structures

  公开了合成多环去甲二萜内酯的对映选择性和非对映选择性方法。采用钯催化的对映选择性烯丙基烷基化来立体选择性地构建所需的手性叔醚并促进 1,3-顺式环戊烯二醇结构单元的合成。精心的底物设计使得在异常温和的条件下通过非对映选择性环丙烷化-Cope重排级联能够聚合十八内酯[6,7,5,5]-四环支架。后期合成中间体的基态能量的计算评估用于指导合成开发并帮助研究这些高度约束和致密的多环结构的构象刚性。这项工作代表了首次成功合成了呋喃丁烯酸内酯衍生的多环去甲松香二萜天然产物家族中任何成员的核心结构。先进的合成操作产生了一系列类似天然产物的化合物，这些化合物被证明具有白细胞介素 5 或白细胞介素 17 的选择性分泌拮抗作用。这种生物活性与已知的亚麻酸内酯的抗白血病活性形成鲜明对比，表明去甲松香素天然产物核心可以作为开发多种治疗方法的有用支架。
• Catalytic enantioselective total synthesis of (+)-eucomic acid
  作者：Benzi I. Estipona、Beau P. Pritchett、Robert A. Craig、Brian M. Stoltz

  DOI：10.1016/j.tet.2016.02.059

  日期：2016.6

  A catalytic enantioselective synthesis of (+)-eucomic acid is reported. A palladium-catalyzed asymmetric allylic alkylation is employed to access the chiral tetrasubstituted α-hydroxyacid moiety found in the natural product. The protecting group strategy was investigated, and a protecting group manipulation was made without any appreciable deleterious effects in the allylic alkylation reaction. Non-natural

  报道了（+）-杜仲酸的催化对映选择性合成。钯催化的不对称烯丙基烷基化反应可用于获得天然产物中的手性四取代α-羟酸部分。研究了保护基策略，并进行了保护基操作，在烯丙基烷基化反应中没有任何明显的有害作用。非天然（+）-杜仲酸以最长的13个步骤的线性序列合成。