60509-83-3

Upstream product

• 29038-91-3 1,2-dichloroadamantane 
• 65567-06-8 lithium diphenylphosphide 
• 33803-54-2 1,2-dibromoadamantane 
• 39257-31-3 1,2-di-iodoadamantane 
• 57680-77-0 adamantylmagnesium bromide 
• 1079-66-9 chloro-diphenylphosphine 
• 35537-98-5 1-bromo-3-chloroadamantane 
• 34676-89-6 diphenylphosphide ion 
• 876-53-9 1,3-dibromoadamantane 
• 16104-50-0 1,3-dichloroadamantane 
• 935-56-8 1-chloroadamantane 
• 4376-01-6 sodium diphenylphosphide 
• 768-90-1 1-Adamantyl bromide 
• 829-85-6 diphenylphosphane 

Relevant academic research and scientific papers

REACTIONS OF 1,3-DIHALOADAMANTANES WITH DIPHENYLPHOSPHIDE IONS BY THE SRN1 MECHANISM. COMPETITION BETWEEN INTERMOLECULAR AND INTRAMOLECULAR ELECTRON TRANSFER REACTIONS

The reactivity of 1,3-dihaloadamantanes with diphenylphosphide ions (Ph2P-) in liquid ammonia was studied. 1,3-Dichloroadamantane (1a), 1-bromo-3-chloroadadmantane (1b) and 1,3-dibromoadamantane (1c) reacted with Ph2P- ions under photostimulation by the SRN1 mechanism.Irradiation of 1c without Ph2P- ions gave no reaction (-. (3b-.); whereas 3a (3b) were formed by intermolecular ET of this radical anion to the substrates.It was observed that the product distribution depends on the substrate and reaction conditions.

Synthesis method of compound with phosphine chirality and axial chirality

The invention relates to a synthesis method of a compound with phosphine chirality and axial chirality. The method comprises the following steps: in an organic solvent system, synthesizing by taking a diaryl phosphine oxide compound and diaryl alkyne as basic raw materials under the effect of an iridium catalyst, an oxidizing agent and a chiral amide ligand, and carrying out post-treatment on a reaction solution to obtain the compound with phosphine chirality and axial chirality. The diaryl phosphine oxide used in the reaction is simple and easy to synthesize, the universality of the substrate is better, the reaction operation is simple and convenient, and the efficiency is high. Synthesis of a ligand is relatively convenient, the ligand is combined with metal in the reaction, and the C-H bond on a benzene ring is selectively activated under the guidance of phosphine oxide of the substrate, so that the carbon-hydrogen bond activation arylation reaction among molecules is realized, and the compound with phosphine chirality and axial chirality is synthesized with medium or more yield and relatively high enantioselectivity. The obtained product can be used as a medical intermediate or a chiral ligand; and the trivalent phosphine obtained by further reducing the product can also be used as a chiral phosphine ligand.

Defying Stereotypes with Nanodiamonds: Stable Primary Diamondoid Phosphines

Direct unequal C-H bond difunctionalization of phosphorylated diamantane was achieved in high yield from the corresponding phosphonates. Reduction of the functionalized phosphonates provides access to novel primary and secondary alkyl/aryl diamantane phos

Electrophilic routes to tertiary adamantyl and diamantyl phosphonium salts

In highly nonpolar media both 1-adamantyl and 1-diamantyl triflates are sufficiently stable to react with nucleophiles in a controlled manner. Several tertiary phosphonium triflate salts with a single adamantyl or diamantyl residue were prepared directly

Synthesis of several halobisnoradamantane derivatives and their reactivity through the SRN1 mechanism

Several bridgehead halobisnoradamantane derivatives (5, 7, 10, and 17) were synthesized from tricyclic diester 1 in good yields using standard methods. The reactivity through the SRN1 mechanism of the above compounds and the known halobisethano derivatives 24 and 25a-c was studied. Iodo derivatives 7, 10, and 25a reacted with diphenylphosphide ions in DMSO under irradiation to give the corresponding substitution and reduction products by the SRN1 mechanism, while iodo ketone 17 gave a mixture of the rearranged substitution product 36 and the reduction product 18. Formation of 36 takes place through a 1,5-hydrogen migration of the initially formed radical, a kind of process that has been observed for the first time in the SRN1 propagation steps. The diiodo derivative 24 reacted with diphenylphosphide ions under similar reaction conditions to give the substitution and/or reduction products 32, 31, 27, 25a, and 26. The intramolecular ET reaction in the monosubstitution radical anion 32?- seems to be faster than the intermolecular ET to the substrate, and the monoiodo derivative 25a is a reaction intermediate.

Reactions of 1- and 2-Halo and 1,2-Dichloroadamantanes with Nucleophiles by the SRN1 Mechanism

2-Bromoadamantane (2-BrAd) reacted in liquid ammonia under irradiation with diphenylphosphide (Ph2P-) ions whereas 2-chloroadamantane (2-ClAd) did not under the same experimental conditions. However, 2-ClAd yielded 2-(trimethylstannyl)adamantane in its photostimulated reaction with trimethylstannyl (Me3Sn-) ions. The compound 1-ClAd yielded the substitution product in a photostimulated slow reaction when the nucleophile is Ph2P- ion; the reaction occurs faster with the nucleophile Me3Sn- ion. All these reactions can be explained by the SRN1 mechanism as they did not occur in the dark and were inhibited by p-dinitrobenzene when photostimulated. In competition experiments, 1-haloadamantane showed more reactivity than 2-haloadamantane. Either with Ph2P- or Me3Sn- ions, 1-BrAd is 1.4 times more reactive than 2-BrAd while 1-ClAd is 12 times more reactive than 2-ClAd with Me3Sn- ions. In the photostimulated reaction of 1,2-dichloroadamantane (7) with Ph2P- the monosubstitution products 1-adamantyldiphenylphosphine (64%) and 2-adamantyldiphenylphosphine (15%) were formed, isolated as the oxides. From these results, it appears that when 7 receives an electron, the 1-position fragments ca. four times faster than the 2-position. The disubstitution product was not formed with Ph2P- ions, but when 7 reacted with a nucleophile having less steric bulk such as a Me3Sn- ion, the 2-chloro-1-(trimethylstannyl)-adamantane and the disubstitution product 1,2-bis(trimethylstannyl)adamantane were formed. The formation of these products is explained in terms of the different rates of the electron transfer reactions of the radical anion intermediates.

Phosphides and Arsenides as Metal-Halogen Exchange Reagents. Part 1. Dehalogenation of Aliphatic Dihalides

Lithium diphenylphosphide and arsenide have been investigated as reagents for metal-halogen exchange.Reactions involving two molar equivalents of the anions with 1,2-dibromoethylenes lead to moderate to good yields of acetylenes and smaller yields of phosphorus-containing by-products.Similar reactions with 2,3-dichlorobuta-1,3-diene and 2-chlorobuta-1,3-diene give SN2' rather than direct substitution products.Evidence is presented that adamantene is an initial product in the reaction of lithium diphenylphosphide with 1,2-di-iodo- and 1,2-dibromo-adamantane, but not with 1,2-dichloroadamantane, although 1- and 2-adamantyldiphenylphosphine oxides are formed in every case.Finally reactions of phosphide anion with geminal dihalides were briefly investigated; 1,1-dibromo-2,2-diphenylethylene gave diphenylacetylene as the major product.

Reaction of 1-Bromoadamantane with Diphenylphosphide and Diphenylarsenide Ions by the SRN1 Mechanism. Facile Nucleophilic Substitution at the Bridgehead Position

The photostimulated reaction of 1-bromoadamantane (1) with diphenylphosphide (2) and diphenylarsenide (6) ions in liquid ammonia afforded good yields of the substitution products, together with small amounts of adamantane (4) and 1,1'-biadamantyl (5) as byproducts.The reaction of 1 with 2 in the dark did not occur, but stimulation with solvated electrons gives a small amount of the substitution product and 5, with a large amount of 4.The photostimulated reaction of 1 with 2 is inhibited by p-dinitrobenzene and di-tert-butyl nitroxide.All these results suggest that these reactions occur by the SRN1 mechanism of substitution, where radical and radical anions are intermediates.