500103-26-4

Usage

Uses

1. Asymmetric Hydrovinylation:
N,N-Bis-[(R)-1-phenylethyl]dibenzo[d,f][1,3,2]dioxaphosphepin-6-amine is used as a catalyst in the asymmetric hydrovinylation of 1,3-dienes. This application takes advantage of the compound's ability to facilitate the addition of vinyl groups to a molecule in a stereoselective manner, which is crucial for the synthesis of enantiomerically pure compounds with specific biological activities.
2. 1,4-Asymmetric Conjugate Addition:
N N-BIS-[(R)-1-PHENYLETHYL]DIBENZO[D F][ is also used in the 1,4-asymmetric conjugate addition of 3-substituted cyclohexenones, which is catalyzed by copper. In this process, the N,N-Bis-[(R)-1-phenylethyl]dibenzo[d,f][1,3,2]dioxaphosphepin-6-amine acts as a ligand, enhancing the selectivity and efficiency of the reaction. This application is particularly relevant in the synthesis of complex organic molecules with specific stereochemistry, which are often found in pharmaceuticals and agrochemicals.

InChI:InChI=1/C28H26NO2P/c1-21(23-13-5-3-6-14-23)29(22(2)24-15-7-4-8-16-24)32-30-27-19-11-9-17-25(27)26-18-10-12-20-28(26)31-32/h3-22H,1-2H3/t21-,22-/m1/s1

Upstream product

• 1806-29-7 2,2'-dihydroxybiphenyl 
• 10024-74-5 (R,R)-N,N-bis-(1-phenylethyl)amine 
• 777067-26-2 [(R,R)-bis(α-methylbenzyl)amino]phosphorous dichloride 
• 16611-68-0 6-chloro-dibenzo[d,f][1,3,2]-dioxaphosphepin 

Relevant academic research and scientific papers

Ligand-induced acceleration of the intramolecular [3 + 2] cycloaddition between alkynes and alkylidenecyclopropanes

(Chemical Equation Presented) Bulky phosphite L6 and several sterically robust phosphoramidites are excellent ligands for promoting the Pd-catalyzed [3 + 2] intramolecular cycloaddition between alkylidenecyclopropanes and alkynes. The use of th

Tunable phosphoramidite ligands for asymmetric hydrovinylation: Ligands par excellence for generation of all-carbon quaternary centers

α-Alkylstyrenes undergo efficient hydrovinylation (addition of ethene) in the presence of a nickel catalyst prepared from [(allyl)NiBr] 2, Na+[BAr4]- [Ar = 3,5-bis(trifluoromethyl)phenyl], and a phosphoramidite ligand giving products in excellent yields and enantioselectivities. In many cases phosphoramidites derived from achiral 2,2′-biphenol are almost as good as ligands derived from the more expensive enantiopure 1,1′-bi(2-naphthol)s. The hydrovinylation products, which carry two versatile latent functionalities, an aryl and a vinyl group, are potentially useful for the synthesis of several important natural products containing benzylic all-carbon quaternary centers. Georg Thieme Verlag Stuttgart.

Rh-catalyzed enantioselective conjugate addition of arylboronic acids with a dynamic library of chiral tropos phosphorus ligands

A library of 19 chiral tropos phosphorus ligands, based on a free-to-rotate (tropos) biphenol unit and a chiral P-bonded alcohol (11 phosphites, 1-P(O)2O to 11-P(O)2O) or secondary amine (8 phosphoramidites, 12-P(O)2N to 19-P(O)2N). were screened, individually and in combinations of two, in the rhodium-catalyzed asymmetric conjugate addition of arylboronic acids to enones and enoates. High enantioselectivities (up to 99% ee) and excellent yields were obtained in the addition to either cyclic or acyclic substrates. The flexible biphenolic P ligands outperformed the analogous rigid binaphtholic P ligands. Variable-temperature 31P NMR studies revealed that the biphenolic ligands are tropos even at low temperature. Only below 190 K was a coalescence observed: upon further cooling, two atropisomers were detected. The Rh homocomplexes ([Rh(La)2]+) were also studied: in general, a single doublet (P-Rh coupling) was observed in the case of the biphenolic phosphite ligands, over the temperature range 380-230 K, demonstrating their tropos nature in the rhodium complexes even at low temperatures. On the other hand, the phosphoramidites showed different behaviors depending on the structure of the ligand and on the nature of the rhodium source. The spectrum at 230 K of the mixture of [Rh(acac)(eth)2] (eth = C2H4) with phosphite 6-P(O)2O and phosphoramidite 19-P(O)2N (the most enantioselective ligand combination in the conjugate addition reaction) revealed the presence of four homocomplexes (total approximately 40%: [Rh(6-P(O)2}2], [Rh{(aR)-19-P(O)2N}2], [Rh((aS)-19-P(O)2N) 2], [Rh((aR)-19-P(O)2N}((aS)-19-P(O)2N}]) and one heterocomplex, [Rh{6-P(O)2O){(aR)-19-P(O)2NJ] (approximately 60%) In the heterocomplex, the biphenol-derived phosphite is free to rotate (tropos) while the biphenol-derived phosphoramidite shows a temperature-dependent tropos/atropos behavior (coalescence temperature = 310 K).

Copper-catalyzed asymmetric conjugate addition of trialkylaluminium reagents to trisubstituted enones: Construction of chiral quaternary centers

Me3Al, Et1Al, and vinylalane species undergo enantioselective conjugate addition to a wide range of 2- or 3-substituted enones (cyclopent-2enones, cyclohex-2-enones, 3-methyl cyclohept-2-enone) in the presence of catalytic amount of copper salt (copper thiophene carboxylate, [Cu(CH3-CN)4]BF4 or [CuOTf]2· C6H6) and tropos-phosphoramidite-based ligand. Thus, chiral quaternary centers can be built, with up to 98% ee after rigorous optimization of experimental conditions. It was shown that the main important parameter was the order of the introduction of the reagents. Then, the generated enantioenriched aluminium enolates and the chiral conjugate adducts were functionalized and used for subsequent reactions.

Rh-catalyzed asymmetric hydrogenation of prochiral olefins with a dynamic library of chiral TROPOS phosphorus ligands

A library of 19 chiral tropos phosphorus ligands, based on a flexible (tropos) biphenol unit and a chiral P-bound alcohol (11 phosphites) or secondary amine (8 phosphoramidites), was synthesized. These ligands were screened, individually and as a combination of two, in the rhodium-catalyzed asymmetric hydrogenation of dehydro-α-amino acids, dehydro-β-amino acids, enamides and dimethyl itaconate. ee values up to 98% were obtained for the dehydro-α-amino acids, by using the best combination of ligands, a phosphite [4-P(O)2O] and a phosphora midite [13-P(O)2N]. Kinetic studies of the reactions with the single ligands and with the combination of phosphite [4-P(O)2O] and phosphoramidite [13-P(O) 2N] have shown that the phosphite, despite being less enantioselective, promotes the hydrogenation of methyl 2-acetamidoacrylate and methyl 2-acetamidocinnamate faster than the mixture of the same phosphite with the phosphoramidite, while the phosphoramidite alone is much less active. In this way, the reaction was optimized by lowering the phosphite/phosphoramidite ratio (the best ratio is 0.25 equiv phosphite/1.75 equiv phosphoramidite) with a resulting improvement of the product enantiomeric excess. A simple mathematical model for a better understanding of the variation of the enantiomeric excess with the phosphite/ phosphoramidite ratio is also presented.

Enantioselective conjugate addition of phenylboronic acid to enones catalysed by a chiral tropos/atropos rhodium complex at the coalescence temperature

A highly enantioselective rhodium-catalysed conjugate addition of phenylboronic acid to cyclic enones has been achieved using a dynamic library of chiral phosphorus ligands; the tropos/atropos nature of the ligands in the rhodium complex has been characterised via 31P-NMR. The Royal Society of Chemistry 2005.

Enantioselective copper-catalyzed conjugate addition to trisubstituted cyclohexenones: Construction of stereogenic quaternary centers

Trimethyl- and triethylaluminum undergo enantioselective conjugate addition to 3-and 2-substituted cyclohexenones in the presence of catalytic amounts of a Cu salt and a phosphoramidite ligand L* (see scheme). Thus, chiral quaternary centers can be built with up to 96.6% ee. Functionalized enones lead to bicyclic structures by a subsequent aldol reaction.