7-phenyldinaphtho<2,1-b:1',2'-d>phosphole | 149639-52-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 7-phenyldinaphtho<2,1-b:1',2'-d>phosphole
• 英文别名: 7-phenyldinaphtho(2,1-b;1',2'-d)phosphole；7-Phenyl-7H-7-phospha-dibenzo[c,g]fluorene；12-phenyl-12-phosphapentacyclo[11.8.0.02,11.03,8.016,21]henicosa-1(13),2(11),3,5,7,9,14,16,18,20-decaene
• CAS: 149639-52-1
• 化学式: C₂₆H₁₇P
• 分子量: 360.395
• InChiKey: SBTIZNBSOGFFKZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  27
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  7-phenyldinaphtho<2,1-b:1',2'-d>phosphole 在 氯代叔丁烷 、 lithium 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 13.0h， 生成 7-(2-methylbutyl)dinaphtho<2,1-b:1',2'-d>phosphole oxide
  参考文献：
  名称：

  Synthesis, Crystal Structure, Dynamic Behavior and Reactivity of Dinaphtho[2,1-b:1',2'-d]phospholes and Related Atropisomeric Phosphacyclic Derivatives

  摘要：

  7-Phenyldinaphtho[2,1-b:1',2'-d]phosphole (1b) has been prepared by reaction of dichlorophenylphosphine either with 2,2'-dilithio-1,1'-binaphthalene or with bis-dialin 7. In the latter case the relevant tetrahydro derivative 8 is formed at the same time. Displacement of the phenyl substituent in Ib by alkyl groups can be accomplished through a dephenylation-alkylation protocol involving a lithium-promoted phosphole anion formation. By this way the unsubstituted phosphole la and a variety of alkyl-substituted derivatives have been prepared. The X-ray crystal structure of Ib shows an intracyclic C-P-C angle of 89.3 degrees indicating that phosphole ring is strained. Alkylphospholium iodides 4 undergo ready ring opening by reaction with LiAlH4 or other nucleophiles under mild conditions affording with fair diastereoselectivities (2-(1,1'-binaphthylyl))substituted phosphines 5 or phosphines oxides 6, respectively. Dinaphthophospholes 1 are fluxional at ambient temperature because of the rapid interconversion of the atropisomeric conformers. Line shape analysis of the variable temperature NMR spectra lead to estimation of an energy barrier of 55-60 kJ mol(-1) for this process. Fluxionality is maintained both when the phosphorus center is tetrasubstituted, like in the relevant oxides 2, and when it is coordinated to a transition metal, like in the Pd-complexes 10. On the contrary, P-substituted dinaphthophosphepines 9 do not undergo atropisomerization even well above room temperature and can be successfully resolved under ambient conditions. The crystal structures of the P-phenyl-substituted derivatives 1b, 8 and 9a, as determined by X-ray diffraction, show remarkable differences in the relative disposition of the naphthalene rings.

  DOI：

  10.1021/jo00100a044
• 作为产物：
  描述：

  (S)-BINAP monoxide 在 正丁基锂 、 三甲基氯硅烷 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 3.0h， 以57%的产率得到7-phenyldinaphtho<2,1-b:1',2'-d>phosphole
  参考文献：
  名称：

  Preparation of Enantiomerically Pure 2‘-Substituted 2-Diphenylphosphino-1,1‘-binaphthyls by Reductive Cleavage of the Carbon−Phosphorus Bond in a Borane Complex of 2-Diphenylphosphino-2‘-diphenylphosphinyl-1,1‘-binaphthyl

  摘要：

  Reaction of (S)-2'-boranatodiphenylphosphino-2-diphenylphosphinyl-1,1'-binaphthyI (3, borane complex of BINAP monoxide) with an excess of n-butyllithium in THF at -78 degreesC brought about a selective cleavage of the carbon-phosphorus bond between the binaphthyl and diphenylphosphinyl groups to generate the binaphthyllithium 14, the treatment of which with electrophiles MeOD, I-2, and ClSnMe3 gave, after removal of the borane, the corresponding 2'-substituted 2-diphenylphosphino-1,1'-binaphthyls (E-MOP 9: E = D, I, SnMe3), without loss of the enantiomeric purity.

  DOI：

  10.1021/jo010691x

文献信息

• Atropisomerism in (±)-7-methyl- and -phenyl-substituted dinaphtho[2,1-b;1′,2′-d]phospholes and dinaphth[2,1-b;1′,2′-d]arsoles
  作者：Andrew A. Watson、Anthony C. Willis、S.Bruce Wild

  DOI：10.1016/0022-328x(93)80189-i

  日期：1993.2

  dinaphtho[2,1-b;1′,2′-d]phospholes and dinaphth[2,1-b:1′,2′-d]arsoles. The molecules are fluxional on the NMR time scale with similar barriers between the conformational isomers (atropisomers) for the four compounds, vis. †G‡ = 56 ± 1 (243 K, ER = PMe), 56 ± 1 (254 K, ER = PPh), 65 ± 1 (287 K, ER = AsMe), 59 ± 1 (259 K, ER = AsPh) kJ mol−1. An X-ray diffraction study of (S)-7-phenyldinaphth[2,1-b;1′,2′-d]arsole

  2，2'-二硫代-1,1'-联萘与RECl 2（E = P或As； R = Me或Ph）反应，得到相应的（±）-7-取代的萘并[2,1- b]； 1'，2'- d ]磷脂和dinaphth [2,1- b：1'，2'- d ]鞋底。该分子可用于四种化合物fluxional上与构象异构体（阻转异构体）之间类似屏障的NMR时间尺度，可见。† G ‡= 56±1（243 K，ER = PMe），56±1（254 K，ER = PPh），65±1（287 K，ER = AsMe），59±1（259 K，ER = AsPh） ）kJ mol -1。（S）-7-苯基二萘酚[2,1- b ; 1'，2'- d的X射线衍射研究通过自发析出结晶的] arsole揭示了扭曲的萘基残基彼此明显弯曲。不对称unidentates（±）-L坐标中的类型的复合物的铁（II）[（η 5 -C 5 H ^ 5）〔1,2-C
• One-pot synthesis of binaphthyl-based phosphines via direct modification of BINAP
  作者：Jing-Jing Ye、Jian-Qiu Zhang、Shigeru Shimada、Li-Biao Han

  DOI：10.1016/j.tetlet.2021.153489

  日期：2021.12

  Herein reported is the convenient and efficient strategy for the preparation of binaphthyl-based phosphines through direct modification to the commercially available 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) with sodium. In the absence of 15-crown-5-ether, a cyclic sodium dinapthylphospholide intermediate is mainly generated. With 15-crown-5-ether, P-Ph bonds are selectively cleft by Na to

  本文报道了通过用钠直接修饰市售的 2,2'-双(二苯基膦)-1,1'-联萘 (BINAP) 来制备联萘基膦的方便有效的策略。在没有 15-crown-5-ether 的情况下，主要生成环状二萘基磷酸钠中间体。使用 15-crown-5-ether 时，P-Ph 键被 Na 选择性裂解以产生基于联萘的磷化二钠。提出了选择性形成二萘基磷化钠或联萘基磷化二钠的机理。
• Study of the Reaction of Bulky Aryllithium Reagents with 3,4-Dimethyl-2,5-diphenyl-1,3,2-oxazaphospholidine-2-borane Derived from Ephedrine
  作者：Michel (Massoud S.) Stephan、Damjan Šterk、Barbara Modec、Barbara Mohar

  DOI：10.1021/jo7014505

  日期：2007.10.1

  by others. In fact, several 2,6-disubstituted aryl groups were successfully appended to the phosphorus atom, furnishing the corresponding (N-ephedrino)phosphine boranes 2a−g with dr >99:1. However, when the attack on the phosphorus atom is hindered, deprotonation on the benzylic position occurs, leading to the formation of enantiomerically pure trans-(N-methylamino)(phenyl)(1-phenyl-1-propenyloxy)phosphine-P-borane

  研究了对映体纯的3,4-二甲基-2,5-二苯基-1,3,2-氧杂氮磷吡啶-2-硼烷（1）与各种笨重的芳基锂试剂的开环。我们的结果与他人获得的结果并不完全一致。实际上，几个2，6-二取代的芳基成功地连接到了磷原子上，从而为dr（99：1 ）提供了相应的（N- ephedrino）膦硼烷2a - g。然而，当在磷原子上的攻击受到阻碍，在苄基位置的去质子化发生，从而导致对映异构纯的形成反式- （Ñ甲基氨基）（苯基）（1-苯基-1-丙烯基氧基）膦P -硼烷（3）。虽然2,2'-二锂-1,1'- biarenes引线攻击到相应的（P -苯基）磷杂环衍生物（4I，Ĵ）和[双（Ñ -ephedrino）]（苯基）膦P -硼烷（5），1,1'- dilithiometallocenes（M =铁，钌）引线攻击的1,1'-双可分离的非对映体混合物[（ñ -ephedrino）（苯基）膦基P -硼烷]的金属茂（2k，l
• Phospholyl(borane) Amino Acids and Peptides: Stereoselective Synthesis and Fluorescent Properties with Large Stokes Shift
  作者：Mathieu Arribat、Emmanuelle Rémond、Sébastien Clément、Arie Van Der Lee、Florine Cavelier

  DOI：10.1021/jacs.7b10954

  日期：2018.1.24

  The synthesis of phospholyl(borane) amino acids was stereoselectively achieved by reaction of phospholide anion with iodo α-amino ester derived from l-aspartic acid or l-serine, followed by in situ complexation with borane. Phospholyl(borane) amino acids are easy to store and can be subjected to direct transformation into the corresponding free phospholyl, gold complex, oxide or sulfur derivatives as

  通过磷脂阴离子与衍生自 l-天冬氨酸或 l-丝氨酸的碘 α-氨基酯反应，然后与硼烷原位络合，立体选择性地合成磷酰（硼烷）氨基酸。磷酰（硼烷）氨基酸易于储存，可直接转化为相应的游离磷酰、金络合物、氧化物或硫衍生物以及磷盐，从而提供多种侧链。在羧基功能或胺的选择性脱保护后，C-或N-肽与丙氨酸部分偶联证明可能掺入肽中。这种磷酰氨基酸和肽衍生物表现出具有大斯托克斯位移 (160 nm) 和荧光高达 535 nm 的荧光特性，这取决于磷酰芳香性和化学环境。
• Dinaphtho[2,1-b; 1′,2′-d]phospholes: a new class of atropisomeric phosphorus ligands
  作者：Antonio Dore、Davide Fabbri、Serafino Gladiali、Ottorino De Lucchi

  DOI：10.1039/c39930001124

  日期：——

  The parent and some alkyl and aryl substituted dinaphtho[2,1-b; 1′,2′-d]phospholes 1 have been synthesized and shown to be atropisomerically stable below room temperature.

  母体和一些烷基和芳基取代的二萘并[2,1-b； 1-,2-d]磷化合物 1 已被合成并显示在室温以下具有阻转异构性稳定。