(6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamant-9-yl)P(BH3)(H) | 587831-80-9

• 英文名称: (6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamant-9-yl)P(BH3)(H)
• 英文别名: (1,3,5-tetramethyl-4,6,8-trioxa-2-phosphaadamantane)BH3；CgPH.(BH3)；2-phosopha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3.7}]decane borane；1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantane borane
• CAS: 587831-80-9
• 化学式: C₁₀H₂₀BO₃P
• 分子量: 230.052
• InChiKey: OJXQVRQJNWEJNO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamant-9-yl)P(BH3)(H) 、 2-溴丙烷 在 butyllithium 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamantyl((i)Pr)BH3
  参考文献：
  名称：

  General Routes to Alkyl Phosphatrioxaadamantane Ligands

  摘要：

  The secondary phosphine CgPH (CgP = 6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamantyl group) is made in 50% yield by a modification of the literature method (avoiding high pressures of PH3) by bubbling PH3 through an acidified solution of 2,4-pentanedione at 0 degrees C. Under similar conditions the ethyl analogue (Et)CgPH is formed from 3,5-heptanedione in 75% yield. The halophosphines CgPCl and CgPBr are made by treatment of CgPH with N-halosuccinimide. CgPBr is also made by treatment of CgPH with Br-2. Three methods are described for the synthesis of CgPR, where R = alkyl: (a) the previously reported acid-catalyzed condensation reaction of RPH2 with 2,4-pentanedione, which has been extended to R = Pr-i; (b) treatment of CgP(BH3)Li with RX followed by borane deprotection with Et2NH, which has been used for R = Pr-i, benzyl, n-C20H41; (c) treatment of CgPBr with RMgX, which has been used for R = Pr-i, Me. The complexes [PtC12(CgPH)(2)] (1), [PdCl2(CgPH)(2)] (2), [PdCl2(CgPR)(2)] (where R = Pr-i (3a), Cy (3b)), and [PtCl2(CgPR)(2)] (where R = Pr-i (4a), Cy (4b), n-C20H41 (4c)) are described. The crystal structures of CgPH, CgPCl, [CgP(CH2Ph)(2)]Br, CgP(n-C20H41), and complexes 1, 3b, and 4c are reported. From the v(CO) values for trans-[RhCl(CO)(CgPX)(2)], the sigma-donor/pi-acceptor properties of CgPX are in the order X = Pr-i > Me > Ph > H > Cl.

  DOI：

  10.1021/om800141y
• 作为产物：
  描述：

  2,4,6-三氧杂-1,3,5,7-四甲基-8-磷杂金刚烷 在 硼烷 作用下， 以 四氢呋喃 为溶剂， 反应 4.08h， 以86%的产率得到(6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamant-9-yl)P(BH3)(H)
  参考文献：
  名称：

  [EN] ALKOXYCARBONYLATION OF VYNIL ESTERS
  [FR] ALCOXYCARBONYLATION D'ESTERS VINYLIQUES

  摘要：

  一种用于烯丙酸酯的烷氧羰基化的方法，包括在存在一种烷醇和一个催化剂体系的情况下，将烯丙酸酯与一氧化碳反应。所述方法中使用的催化剂体系可通过组合以下物质获得：a) VIII B族金属或其化合物，以及b) 一种一般式(I)的双齿配体，其中，R是一个共价桥接基团；R1与其连接的Q2共同形成一个可选择地取代的2-Q2-三环[3.3.1.1 {3,7}]癸基团或其衍生物(2-PA)；R2和R3独立地代表最多20个原子的一价基团，或共同形成最多20个原子的二价基团；Q1和Q2各自独立地代表磷、砷或锑。该方法用于生产式(II) CH2 (OH)CH2 C(O) OR28的3-羟基丙酸酯或酸。该方法也可用于生产式(III)的乳酸酯或酸。

  公开号：

  WO2005118519A1

文献信息

• Diphosphanes derived from phobane and phosphatrioxa-adamantane: similarities, differences and anomalies
  作者：Deborah L. Dodds、Joelle Floure、Michael Garland、Mairi F. Haddow、Thomas R. Leonard、Claire L. McMullin、A. Guy Orpen、Paul G. Pringle

  DOI：10.1039/c1dt10335k

  日期：——

  The homodiphosphanes CgP–PCg (1) and PhobP–PPhob (2) and the heterodiphosphanes CgP–PPhob (3), CgP–PPh2 (4a), CgP–P(o-Tol)2 (4b), CgP–PCy2 (4c), CgP–PtBu2 (4d), PhobP–PPh2 (5a), PhobP–P(o-Tol)2 (5b), PhobP–PCy2 (5c), PhobP–PtBu2 (5d) where CgP = 6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamant-9-yl and PhobP = 9-phosphabicyclo[3.3.1]nonan-9-yl have been prepared from CgP(BH3)Li or PhobP(BH3)Li and the appropriate halophosphine. The formation of 1 is remarkably diastereoselective, with the major isomer (97% of the product) assigned to rac-1. Restricted rotation about the P–P bond of the bulky meso-1 is detected by variable temperature 31P NMR spectroscopy. Diphosphane 3 reacts with BH3 to give a mixture of CgP(BH3)–PPhob and CgP–PPhob(BH3) which was unexpected in view of the predicted much greater electron-richness of the PhobP site. Each of the diphosphanes was treated with dimethylacetylene dicarboxylate (DMAD) in order to determine their propensity for diphosphination. The homodiphosphanes 1 and 2 did not react with DMAD. The CgP-containing heterodiphosphanes 4a–d all added to DMAD to generate the corresponding cisalkenes CgPCH(CO2Me)CH(CO2Me)PR2 (6a–d) which have been used in situ to form chelate complexes of the type [MCl2(diphos)] (7a–d) where M = Pd or Pt. The PhobP-containing heterodiphosphanes 3 and 5a–d react anomalously with DMAD and do not give the products of diphosphination. The X-ray crystal structures of the diphosphanes 2, 3, 4a, and 5a, the monoxide and dioxide of diphosphane 1, and the platinum chelate complex 7c have been determined and their structures are discussed.

  同种二膦CgP–PCg（1）和PhobP–PPhob（2）以及异种二膦CgP–PPhob（3）、CgP–PPh2（4a）、CgP–P（o-Tol）2（4b）、CgP–PCy2（4c）、CgP–PtBu2（4d）、PhobP–PPh2（5a）、PhobP–P（o-Tol）2（5b）、PhobP–PCy2（5c）、PhobP–PtBu2（5d）（其中CgP=6-膦-2，4，8-三氧-1，3，5，7-四甲基金刚烷-9-基，PhobP=9-磷双环[3.3.1]壬-9-基）已由CgP（BH3）Li或PhobP（ ）Li与相应的膦卤化物制备得到。1的形成具有显著的非对映选择性，主要异构体（产物97%）被指定为外消旋-1。通过变温31P核磁共振波谱检测到庞大的内消旋-1中的P—P键的旋转受阻。二膦3与 反应得到CgP（ ）–PPhob和CgP–PPhob（ ）的混合物，这与预测的PhobP位点具有更强的给电子性不相符。每种二膦都与二甲基乙炔二羧酸酯（DMAD）反应，以确定其双膦化的倾向。同种二膦1和2不与DMAD反应。含CgP的异种二膦4a～d都与DMAD加成并生成了相应顺式烯烃CgPCH（CO2Me）CH（CO2Me）PR2（6a～d），它们已被用于原位形成螯合型配合物[MCl2（diphos）]（7a～d）（M=Pd或Pt）。含PhobP的异种二膦3和5a～d与DMAD反常地反应且不生成双膦化产物。已测定二膦2、3、4a、5a、1的一氧化物和二氧化物以及铂螯合物7c的X射线晶体结构，并讨论了它们的结构。
• [EN] PROCESS FOR THE CARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS, NOVEL CARBONYLATION LIGANDS AND CATALYST SYSTEMS INCORPORATING SUCH LIGANDS<br/>[FR] PROCÉDÉ DE CARBONYLATION DE COMPOSÉS À INSATURATION ÉTHYLÉNIQUE, NOUVEAUX LIGANDS DE CARBONYLATION, ET SYSTÈMES CATALYSEURS COMPRENANT CES LIGANDS
  申请人：LUCITE INT UK LTD

  公开号：WO2010001174A1

  公开（公告）日：2010-01-07

  A novel bidentate catalytic ligand of general formula (I) is described. R represents a hydrocarbyl aromatic structure having at least one aromatic ring to which Q 1 and Q 2 are each linked, via the respective linking group, if present, on available adjacent atoms of the at least one aromatic ring. The groups X 3 and X 4 represent radicals joined via tertiary carbon atoms to the respective atom Q 1 and the groups X 1 and X 2 represent radicals joined via primary, or substituted aromatic ring carbon atom(s) to the respective atom Q 2. A and B represent an optional lower alkylene linking group. Q 1 and Q 2 each represent phosphorus, arsenic or antimony. A process for the carbonylation of ethylenically unsaturated compounds comprising reacting the compound with carbon monoxide in the presence of a source of hydroxyl groups, optionally, a source of anions and catalyst system obtainable by combining a metal of Group 8, 9 or 10 or a compound thereof and the bidentate ligand of general formula (I) is also described.

  描述了一种一般式(I)的新型双齿催化配体。其中，R代表至少具有一个芳香环的烃基芳香结构，其中Q1和Q2分别通过至少一个芳香环上可用的相邻原子的相应连接基（如果存在）连接。基团X3和X4代表通过第三级碳原子连接到相应原子Q1的基团，基团X1和X2代表通过主要或取代的芳香环碳原子连接到相应原子Q2的基团。A和B代表可选的较低烷基连接基。Q1和Q2分别代表磷、砷或锑。还描述了一种用于乙烯基不饱和化合物的羰基化的方法，包括将该化合物与一氧化碳在羟基源的存在下反应，可选地，与阴离子源和由结合第8、9或10族金属或其化合物以及一般式(I)的双齿配体的催化系统获得的催化剂。