New conformational flexible phosphane and phosphane oxide macrobicycles

Däbritz, Frank; Theumer, Gabriele; Грүнер, Маргит; Бауер, И.

doi:10.1016/j.tet.2009.01.102

Cited by 27 publications

(15 citation statements)

References 26 publications

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“…To our knowledge, only one macrocyclic dibridgehead diphosphine diborane has been previously reported, ( in,in/out , out )- 18 ·2BH 3 in Scheme 9 [ 50 – 51 ]. This features triarylphosphorus bridgeheads and p -phenylene containing tethers that are long enough to allow rapid homeomorphic isomerization.…”

Section: Discussionmentioning

confidence: 99%

“…This features triarylphosphorus bridgeheads and p -phenylene containing tethers that are long enough to allow rapid homeomorphic isomerization. The precursor 18 ·2(=O) was prepared by a threefold Williamson ether synthesis in surprisingly high yields (61% in , in / out , out and in , out combined) [ 50 – 51 ], likely aided by the geminal dialkyl effect associated with the quaternary centers [ 52 ].…”

Section: Discussionmentioning

confidence: 99%

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Non-metal-templated approaches to bis(borane) derivatives of macrocyclic dibridgehead diphosphines via alkene metathesis

Fiedler¹,

Barbasiewicz²,

Stollenz³

et al. 2018

Beilstein J. Org. Chem.

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Two routes to the title compounds are evaluated. First, a ca. 0.01 M CH2Cl2 solution of H3B·P((CH2)6CH=CH2)3 (1·BH3) is treated with 5 mol % of Grubbs' first generation catalyst (0 °C to reflux), followed by H2 (5 bar) and Wilkinson's catalyst (55 °C). Column chromatography affords H3B·P(n-C8H17)3 (1%), H3B·P((CH2)13 CH2)(n-C8H17) (8%; see text for tie bars that indicate additional phosphorus–carbon linkages, which are coded in the abstract with italics), H3B·P((CH2)13 CH2)((CH2)14)P((CH2)13 CH2)·BH3 (6·2BH3, 10%), in,out-H3B·P((CH2)14)3P·BH3 (in,out-2·2BH3, 4%) and the stereoisomer (in,in/out,out)-2·2BH3 (2%). Four of these structures are verified by independent syntheses. Second, 1,14-tetradecanedioic acid is converted (reduction, bromination, Arbuzov reaction, LiAlH4) to H2P((CH2)14)PH2 (10; 76% overall yield). The reaction with H3B·SMe2 gives 10·2BH3, which is treated with n-BuLi (4.4 equiv) and Br(CH2)6CH=CH2 (4.0 equiv) to afford the tetraalkenyl precursor (H2C=CH(CH2)6)2(H3B)P((CH2)14)P(BH3)((CH2)6CH=CH2)2 (11·2BH3; 18%). Alternative approaches to 11·2BH3 (e.g., via 11) were unsuccessful. An analogous metathesis/hydrogenation/chromatography sequence with 11·2BH3 (0.0010 M in CH2Cl2) gives 6·2BH3 (5%), in,out-2·2BH3 (6%), and (in,in/out,out)-2·2BH3 (7%). Despite the doubled yield of 2·2BH3, the longer synthesis of 11·2BH3 vs 1·BH3 renders the two routes a toss-up; neither compares favorably with precious metal templated syntheses.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Non-metal-templated approaches to bis(borane) derivatives of macrocyclic dibridgehead diphosphines via alkene metathesis

Fiedler¹,

Barbasiewicz²,

Stollenz³

et al. 2018

Beilstein J. Org. Chem.

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“…In this context, metal complexes based on P,N-containing heterocycles are of interest, in particular, the cyclic diphosphine ligand P R 2 N R′ 2 (P 2 N 2 stands for a 1,5-R′-3,7-R derivative of 1,5-diaza-3,7-diphosphacyclooctane) contains soft coordination sites that allow a variety of metal complexes to be obtained. [37][38][39][40][41][42][43] These heterocycles can be obtained with various functionalization on the P and N atoms, which can be used to optimize target catalysts activity.…”

Section: Introductionmentioning

confidence: 99%

“…[45] The hypothesis was also proposed that catalytic activity depended on the conformational kinetics: that is, the rate-limiting stage is an intramolecular proton transfer as a result of heterocyclic fragment conversion. [38,50,63,64] However, there are only few papers dealing with the analysis of the intramolecular kinetics of such complexes in solution. [65,67,68] In this work, we try to establish the key factors that control the conformational equilibrium and dynamics of these heterocycles and their metal complexes in solution.…”

Section: Introductionmentioning

confidence: 99%

Conformational Analysis of P,N‐Containing Eight‐Membered Heterocycles and Their Pt/Ni Complexes in Solution

et al. 2016

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“…Based on the results of matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry, one of the fractions was determined as a mixture of isomers of macrobicycle 65 having a cylindrical structure (yield was 8% of the total amount of the macrocycles). 27,38 The single-capping strategy was further developed in the studies, 43,44 where the synthesis of phosphine oxide derivatives of bicyclic cryptands containing ever larger cavities was documented.…”

Section: Synthesis Of Phosphorus-containing Cryptandsmentioning

confidence: 99%

Phosphorus-containing macrocyclic compounds: synthesis and properties

Knyazeva¹,

Бурилов²,

Пудовик³

et al. 2013

Russ. Chem. Rev.

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Main trends in the development of methods for Main trends in the development of methods for the synthesis of phosphorus-containing macrocyclic com-the synthesis of phosphorus-containing macrocyclic compounds in the past 15 years are considered. Emphasis is pounds in the past 15 years are considered. Emphasis is given to reactions producing macrocyclic structures with the given to reactions producing macrocyclic structures with the participation of a phosphorus atom and other functional participation of a phosphorus atom and other functional groups involved in organophosphorus molecules and to groups involved in organophosphorus molecules and to modifications of macrocycles by phosphorus compounds modifications of macrocycles by phosphorus compounds in different valence states. Possibilities of the practical in different valence states. Possibilities of the practical application of phosphorus-containing macrocyclic com-application of phosphorus-containing macrocyclic compounds in difference areas of science and engineering are pounds in difference areas of science and engineering are discussed. The bibliography includes 205 references discussed. The bibliography includes 205 references. .

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New conformational flexible phosphane and phosphane oxide macrobicycles

Cited by 27 publications

References 26 publications

Non-metal-templated approaches to bis(borane) derivatives of macrocyclic dibridgehead diphosphines via alkene metathesis

Non-metal-templated approaches to bis(borane) derivatives of macrocyclic dibridgehead diphosphines via alkene metathesis

Conformational Analysis of P,N‐Containing Eight‐Membered Heterocycles and Their Pt/Ni Complexes in Solution

Phosphorus-containing macrocyclic compounds: synthesis and properties

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