(R)-Me-BIPAM

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (R)-Me-BIPAM
• 英文别名: 10-[[13-(dimethylamino)-12,14-dioxa-13-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaen-10-yl]methoxymethyl]-N,N-dimethyl-12,14-dioxa-13-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaen-13-amine
• 化学式: C₄₆H₃₈N₂O₅P₂
• 分子量: 760.766
• InChiKey: OPPSQSBXELPSMR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.4
• 重原子数：
  55
• 可旋转键数：
  6
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  68.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (R)-Me-BIPAM 、 bis(1,5-cyclooctadiene)iridium(I) tetrakis[3,5-bis(trifluoromethyl)phenyl]borate 、 N-(3-(N,N-dimethylaminocarbonylphenyl))-2-oxo-2-phenylacetamide 反应 0.02h， 生成
  参考文献：
  名称：

  阳离子Ir / Me-BIPAM催化的不对称分子内直接加氢芳基化反应的范围和机理研究

  摘要：

  Results of mechanistic studies on asymmetric hydroarylation of alpha-keto amides Via direct C-H bond addition to a carbonyl group catalyzed by a cationic Ir/Me-BIPAM complex are presented in this paper. A catalytic cycle involving C-H bond cleavage to give an Ar-[Ir](+) intermediate, insertion of a carbonyl group into the aryl-iridium bond, giving iridium alkoxide, and finally reductive elimination to reproduce active [Ir](+) species is proposed. The mechanistic insight for the iridium hydride species indicated that the C-H bond cleavage is caused in a reversible manner. Furthermore, the kinetic isotope effect was measured by product analysis of the reaction to compare HID, and it was determined that k(H)/k(D) was 1.85. These experimental results suggest that the C-H bond cleavage step is not included hi the turnover-limiting step. In addition, Hammett studies of substrates (rho = -0.99) demonstrated that electron-donating groups at the para position to the reactive C-H bond accelerate the reaction rate. This linear relationship obtained in the Hammett plot indicates that the nucleophilicity of the aryl-iridium intermediate is an important factor in this reaction. All of the data indicate that carbonyl insertion into aryl-iridium is included in the turnover-limiting step of the catalytic cycle.

  DOI：

  10.1021/om501260w
• 作为产物：
  描述：

  三(二甲胺基)膦 、 3,3''-[氧基二(亚甲基)]二-(1S,1''S)-1,1'-联-2-萘酚 在 氯化铵 作用下， 以 甲苯 为溶剂， 反应 12.0h， 以74%的产率得到(R)-Me-BIPAM
  参考文献：
  名称：

  铑（I）-手性亚磷酰胺配合物催化α，β-不饱和羰基化合物对芳基硼酸的对映选择性1,4-加成

  摘要：

  由Shibasaki's联结的-（R）-BINOL和P（NMe 2）3合成手性双齿亚磷酰胺（5a），作为铑（I）催化的芳基硼酸不对称1,4-加成到α，β-的新配体不饱和羰基化合物。充分研究了5a和Feringa单齿亚磷酰胺（4，R 1，R 2  = Et）对产率和对映选择性的影响。在碱例如KOH和Et 3的存在下，反应显着加速N，可在低于50°C的温度下完成反应。在加入到环状烯酮，如2-环戊烯酮，2-环己烯酮，在50℃下在存在2-cycloheptenone的[Rh（COE）2 CL] 2 - 4（R 1，R 2  = ET）复合导致对映选择性高达98％，尽管对无环烯酮（0-70％ee）效果不佳。另一方面，[Rh（nbd）2 ] BF 4和5a之间的络合物在室温下在存在Et 3的情况下于2小时内完成了向环烯酮的加成反应。N的产率为86–99％，ee为96–99.8％。该催化剂对无环烯酮也有

  DOI：

  10.1016/j.jorganchem.2006.04.042
• 作为试剂：
  描述：

  4,6-二甲基-1-苯并呋喃-2,3-二酮 、 4-氟苯硼酸 在 (R)-Me-BIPAM 、 potassium fluoride 、 tris(triphenylphosphine)ruthenium(II) chloride 、 乙腈 作用下， 以 水 、 甲苯 为溶剂， 反应 18.0h， 以96%的产率得到(3S)-3-(4-fluorophenyl)-3-hydroxy-4,6-dimethyl-2,3-dihydro-1-benzofuran-2-one
  参考文献：
  名称：

  Ruthenium–Me-BIPAM-catalyzed addition reaction of aryl-boronic acids to benzofuran-2,3-diones for the enantioselective synthesis of 3-aryl-3-hydroxybenzofuran-2-ones

  摘要：

  We have developed an enantioselective synthesis of 3-aryl-3-hydroxybenzofuran-2-ones via the ruthenium-catalyzed 1,2-addition of arylboronic acids to benzofuran-2,3-diones. The use of RuCl2(PPh3)(3) with a chiral bidentate phosphoramidite ligand [(R,R)-Me-BIPAM] in the presence of a small amount of acetonitrile (20 mol %) gave optically active 3-aryl-3-hydroxybenzofuran-2-ones with up to 96% ee. This reaction is the first example of a catalytic asymmetric 1,2-addition reaction of arylboronic acids to benzofuran-2,3-diones for the highly efficient and enantioselective synthesis of quaternary carbon containing benzofuran-2-ones. (c) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2015.10.010

文献信息

• Chiral Bis-phosphoramidites Based on Linked-BINOL for Rhodium-catalyzed 1,4-Addition of Arylboronic Acids to α,β-Unsaturated Carbonyl Compounds
  作者：Yasunori Yamamoto、Kazunori Kurihara、Noriyuki Sugishita、Kengo Oshita、Dongguo Piao、Norio Miyaura

  DOI：10.1246/cl.2005.1224

  日期：2005.9

  Cationic rhodium(I) complex prepared from Shibasaki’s linked-BINOL and [Rh(nbd)2]BF4 catalyzed asymmetric 1,4-addition of arylboronic acids to enones at room temperature with high enantioselectivities up to 99.8%ee.

  由Shibasaki的联接-BINOL和[Rh(nbd)2]BF4制备的阳离子铑(I)配合物在室温下催化芳基硼酸对烯酮的非对映异构体1,4-加成反应，获得了高达99.8%ee的优秀对映选择性。
• CATALYST FOR ASYMMETRIC SYNTHESIS, LIGAND FOR USE THEREIN, AND PROCESS FOR PRODUCING OPTICALLY ACTIVE COMPOUND THROUGH ASYMMETRIC SYNTHESIS REACTION USING THEM
  申请人：Japan Science and Technology Agency

  公开号：EP1854802A1

  公开（公告）日：2007-11-14

  Compounds represented by the following general formula (1a) or (1b). A complex comprising a center metal of rhodium and a compound represented by the following general formula (1a) or (1b) as a ligand. A catalyst for optically active beta-substituted carbonyl compound synthesis and catalyst for asymmetric 1, 2 addition reaction being composed of the complex. A method of production of an optically active beta-aryl compound from an alpha, beta-unsaturated compound and an aryl-boronic acid derivative and method of production of an optically active aryl alcohol compound from an aldehyde compound and aryl boronic acid derivatives using the catalyst. A complex comprising a center metal of palladium and a compound represented by the following general formula (1a) or (1b) as a ligand. A catalyst for asymmetric allylic substitution reaction being composed of the complex. A method of production of an optically active dialkyl (1,3-disubstituted propeny)malonate compound from a 1,3- disubstituted ally acetate compound and a dialkyl malonate and method of production of an optically active allylamine compound from a 1,3-disubstituted ally acetate compound and an amine compound. The compounds have not only the versatility of being usable in the synthesis of wide-ranging optically active aryl compounds but also the selectivity and reactivity permitting synthesis with high yield within a short period of time under industrially advantageous mild conditions.

  由以下通式(1a)或(1b)代表的化合物。 由中心金属铑和通式(1a)或(1b)代表的化合物作为配体组成的配合物。由该配合物组成的光学活性β-取代羰基化合物合成催化剂和不对称1，2加成反应催化剂。利用该催化剂从α，β-不饱和化合物和芳基硼酸衍生物制取光学活性β-芳基化合物的方法，以及利用该催化剂从醛化合物和芳基硼酸衍生物制取光学活性芳基醇化合物的方法。一种由钯中心金属和作为配体的下式(1a)或(1b)代表的化合物组成的配合物。一种由该配合物组成的不对称烯丙基取代反应催化剂。由 1，3-二取代的乙酸烯丙酯化合物和丙二酸二烷基酯生产光学活性二烷基（1，3-二取代丙 烯）丙二酸酯化合物的方法，以及由 1，3-二取代的乙酸烯丙酯化合物和胺化合物生产光学活性 烯丙基胺化合物的方法。这些化合物不仅具有可用于合成各种光学活性芳基化合物的多功能性，而且还具有选择性和反应性，可在工业上有利的温和条件下在短时间内以高产率合成。
• Method of making tetrahydronaphthyridinyl nonanoic acid compounds
  申请人：SciFluor Life Sciences, Inc.

  公开号：US10253025B2

  公开（公告）日：2019-04-09

  The present application relates to methods of preparing a compound of formula I: or a pharmaceutically acceptable salt or solvate thereof.

  本申请涉及制备式 I 化合物的方法： 或其药学上可接受的盐或溶液的方法。
• Catalyst for Asymmetric Synthesis, Ligand for Use Therein, and Process for Producing Optically Active Compound through Asymmetric Synthesis Reaction Using Them
  申请人：Miyaura Norio

  公开号：US20090156849A1

  公开（公告）日：2009-06-18

  Compounds represented by the following general formula (1a) or (1b). A complex comprising a center metal of rhodium and a compound represented by the following general formula (1a) or (1b) as a ligand. A catalyst for optically active beta-substituted carbonyl compound synthesis and catalyst for asymmetric 1, 2 addition reaction being composed of the complex. A method of production of an optically active beta-aryl compound from an alpha, beta-unsaturated compound and an aryl-boronic acid derivative and method of production of an optically active aryl alcohol compound from an aldehyde compound and aryl boronic acid derivatives using the catalyst. A complex comprising a center metal of palladium and a compound represented by the following general formula (1a) or (1b) as a ligand. A catalyst for asymmetric allylic substitution reaction being composed of the complex. A method of production of an optically active dialkyl (1,3-disubstituted propeny)malonate compound from a 1,3-disubstituted ally acetate compound and a dialkyl malonate and method of production of an optically active allylamine compound from a 1,3-disubstituted ally acetate compound and an amine compound. The compounds have not only the versatility of being usable in the synthesis of wide-ranging optically active aryl compounds but also the selectivity and reactivity permitting synthesis with high yield within a short period of time under industrially advantageous mild conditions.
• METHOD OF MAKING TETRAHYDRONAPHTHYRIDINYL NONANOIC ACID COMPOUNDS
  申请人：SciFluor Life Sciences, Inc.

  公开号：US20190194195A1

  公开（公告）日：2019-06-27

  The present application relates to methods of preparing a compound of formula I: or a pharmaceutically acceptable salt or solvate thereof.