methyl (1S,2R)-1,2-diphenylcyclopropane-1-carboxylate

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: methyl (1S,2R)-1,2-diphenylcyclopropane-1-carboxylate
• 英文别名: (1S,2R)-methyl 1,2-diphenylcyclopropanecarboxylate
• 化学式: C₁₇H₁₆O₂
• 分子量: 252.313
• InChiKey: YAOZVDIKXMRFBG-NVXWUHKLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl (1S,2R)-1,2-diphenylcyclopropane-1-carboxylate 在 potassium tert-butylate 作用下， 以 二甲基亚砜 为溶剂， 以60%的产率得到trans-1,2-diphenyl-1-cyclopropanecarboxylic acid
  参考文献：
  名称：

  D₂-Symmetric Dirhodium Catalyst Derived from a 1,2,2-Triarylcyclopropanecarboxylate Ligand: Design, Synthesis and Application

  摘要：

  Dirhodium tetrakis-(R)-(1-(4-bromophenyl)-2,2-diphenylcyclopropanecarboxylate) (Rh-2(R-BTPCP)(4)) was found to be an effective chiral catalyst for enantioselective reactions of aryl- and styryldiazoacetates. Highly enantioselective cyclopropanations, tandem cyclopropanation/Cope rearrangements and a combined C- functionalization/Cope rearrangement were achieved using Rh-2(R-BTPCP)(4) as catalyst. The advantages of Rh-2(R-BTPCP)(4) include its ease of synthesis, its tolerance to the size of the ester group in the styryldiazoacetates, and its compatibility with clichloromethane as solvent. Computational studies suggest that the catalyst adopts a D-2-symmetric arrangement, but when the carbenoid binds to the catalyst, two of the p-bromophenyl groups on the ligands rotate outward to make room for the carbenoid and the approach of the substrate to the carbenoid.

  DOI：

  10.1021/ja2074104
• 作为产物：
  描述：

  苯乙酸甲酯 在 dirhodium tetrakis(S-(N-dodecylbenzenesulfonyl)prolinate) 、 4-乙酰氨基苯磺酰叠氮 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 、 正戊烷 为溶剂， 反应 26.33h， 生成 methyl (1S,2R)-1,2-diphenylcyclopropane-1-carboxylate
  参考文献：
  名称：

  使用芳基重氮乙酸酯对映选择性二铑 (II) 催化的环丙烷化反应指南

  摘要：

  用于生成环丙烷的催化对映选择性方法长期以来一直是制药业的兴趣所在。手性二铑 (II) 催化剂被证明是生成各种环丙烷库的有效手段。Rh 2 ( R -DOSP) 4通常是重氮乙酸甲酯与苯乙烯的不对称分子间环丙烷化反应最有效的催化剂。Rh 2 ( S -PTAD) 4提供高水平的邻位取代芳基重氮乙酸酯的对映体诱导。不太成熟的 Rh 2 ( R -BNP) 4对 Rh 2 ( R-DOSP) 4和 Rh 2 ( S -PTAD) 4在催化 3-甲氧基取代的重氮基乙酸芳基酯的高度对映选择性环丙烷化反应中。苯乙烯的取代对环丙烷化的不对称诱导仅具有中等影响。

  DOI：

  10.1016/j.tet.2013.04.075

文献信息

• Blue light-promoted N–H insertion of amides, isatins, sulfonamides and imides into aryldiazoacetates: Synthesis of unnatural α-aryl amino acid derivatives
  作者：Celso Y. Okada、Caio Y. dos Santos、Igor D. Jurberg

  DOI：10.1016/j.tet.2020.131316

  日期：2020.12

  A photochemical protocol using blue light allows the N–H insertion of amides, isatins, sulfonamides and imides into aryldiazoacetates to afford the corresponding α-amino esters. This method is experimentally simple, inexpensive and tolerates numerous functional groups, thus allowing the straightforward preparation of a variety of α-aryl amino acid derivatives in good yields.

  使用蓝光的光化学方法可以使酰胺，靛红，磺酰胺和酰亚胺的N–H插入芳基重氮乙酸酯中，得到相应的α-氨基酯。该方法在实验上是简单的，廉价的并且耐受许多官能团，因此允许以良好的产率直接制备多种α-芳基氨基酸衍生物。
• Enantioselective dirhodium(II)-catalyzed cyclopropanations with trimethylsilylethyl and trichloroethyl aryldiazoacetates
  作者：Solymar Negretti、Carolyn M. Cohen、Jane J. Chang、David M. Guptill、Huw M.L. Davies

  DOI：10.1016/j.tet.2015.05.045

  日期：2015.9

  readily prepared by rhodium-catalyzed cyclopropanation of alkenes with aryldiazoacetates and styryldiazoaceates, in which the ester functionality is either trimethylsilylethyl (TMSE) or trichloroethyl (TCE). By having labile protecting groups on the ester, chiral triarylcyclopropane carboxylate ligands were conveniently prepared. The asymmetric induction during cyclopropanation is dependent on the

  通过用芳基重氮乙酸酯和苯乙烯基二重氮酸酯对烯烃进行铑催化的环丙烷化，可以轻松制备高度官能化的环丙烷羧酸酯，其中酯官能度为三甲基甲硅烷基乙基（TMSE）或三氯乙基（TCE）。通过在酯上具有不稳定的保护基，可以方便地制备手性三芳基环丙烷羧酸酯配体。环丙烷化过程中的不对称诱导取决于酯基和手性四羧酸四氢吡啶鎓催化剂的性质。脯氨酸盐催化剂Rh 2（S -DOSP）4是TMSE重氮酯与苯乙烯不对称分子间环丙烷化的最佳催化剂，而Rh 2（R -BPCP）4 是TCE重氮酯的最佳催化剂。
• Highly Regio- and Enantioselective Formal [3 + 2]-Annulation of Indoles with Electrophilic Enol Carbene Intermediates
  作者：Changcheng Jing、Qing-Qing Cheng、Yongming Deng、Hadi Arman、Michael P. Doyle

  DOI：10.1021/acs.orglett.6b02192

  日期：2016.9.16

  formal [3 + 2]-annulation reactions of indoles and electrophilic enol carbenes. High enantioselectivity and exclusive regiocontrol occurred with enoldiazoacetamides using a less sterically encumbered prolinate-ligated dirhodium(II) catalyst in reactions with N-substituted indoles without substituents at the 2- or 3-positions via a selective vinylogous addition process. In this transformation, donor–acceptor

  手性环戊烷稠合的二氢吲哚通过吲哚和亲电子烯醇卡宾的正式[3 + 2]环化反应合成，具有高度的区域控制和对映控制。使用较少空间阻碍的脯氨酸盐连接的二碘（II）催化剂，通过选择性乙烯基醇加成反应，与2-或3-位无取代基的N-取代的吲哚反应，烯醇二乙酰胺发生了高对映选择性和排他性区域控制。在这种转化过程中，由烯丙基重氮乙酰胺生成的供体-受体环丙烯用作卡宾前体，形成金属卡宾中间体。
• Bis(imino)pyridine iron complexes for catalytic carbene transfer reactions
  作者：Ban Wang、Isaac G. Howard、Jackson W. Pope、Eric D. Conte、Yongming Deng

  DOI：10.1039/c9sc02189b

  日期：——

  bis(imino)pyridine iron complex, for the first time, is developed as an effective metal carbene catalyst for carbene transfer reactions of donor-acceptor diazo compounds. Its broad catalytic capability is demonstrated by a range of metal carbene reactions, from cyclopropanation, cyclopropenation, epoxidation, and Doyle-Kirmse reaction to O-H insertion, N-H insertion, and C-H insertion reactions. The

  首次开发了双（亚氨基）吡啶铁配合物，作为供体-受体重氮化合物的卡宾转移反应的有效金属卡宾催化剂。从环丙烷化，环丙烷化，环氧化和Doyle-Kirmse反应到OH插入，NH插入和CH插入反应，金属卡宾反应证明了其广泛的催化能力。新型手性双（亚氨基）吡啶铁催化剂成功地实现了苯乙烯和苯基重氮乙酸甲酯的不对称环丙烷化反应，为金属卡宾反应的手性铁催化的发展提供了新的途径。
• A rigid dirhodium(II) carboxylate as an efficient catalyst for the asymmetric cyclopropanation of olefins
  作者：Sophie K Bertilsson、Pher G Andersson

  DOI：10.1016/s0022-328x(00)00025-5

  日期：2000.5

  The dirhodium(II) complex 7 of (1S,3R,4R)-2-(p-tert-butylphenylsulphonyl)-2-aza-bicyclo[2.2.1]heptane-3-carboxylic acid (3) (or its enantiomer) was synthesised in four steps from cyclopentadiene, (R)- or (S)-phenylethylamine and methyl glyoxylate. Complex 7 was evaluated as a catalyst in the asymmetric cyclopropanation of alkenes with vinyl- and phenyl-diazoesters, resulting in enantioselectivity of

  （1 S，3 R，4 R）-2-（对-叔丁基丁基苯磺酰基）-2-氮杂-双环[2.2.1]庚烷-3-羧酸（3）的二价铑（II）配合物7（3）（或它的对映体）是由环戊二烯，（R）-或（S）-苯乙胺和乙醛酸甲酯分四个步骤合成的。在烯烃与乙烯基和苯基重氮酯的不对称环丙烷化反应中，络合物7被评估为催化剂，对映选择性高达92％。