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An enantioselective synthesis of a new class of benzophosphole-based heterocycles bearing a fused triazole ring with enantioselectivities of ≤99% is reported. The key steps of the synthesis are based on an innovative stereospecific phosphinyl N → O migration of aminophosphine-boranes into phosphinites, followed by an intramolecular cyclization. Five X-ray structures of P-chirogenic triazolobenzophospholes and a gold(I) complex were established, for assigning absolute configurations, the stereochemistry of the reactions, and the placement of the triazole substituent at the syn position of the P center.

We report the synthesis of a new generation of phenoxy-amidine ligands based on an aryloxy moiety possessing an ortho-N -linked trisubstituted amidine. The reaction of the phenol-amidine proligands with aluminum and zinc alkyls gave mono- or bis-ligated complexes depending on the metal/ligand ratio used. The solid-state structure of four proligands and thirteen Zn and Al complexes has been determined by X-Ray diffraction analysis. The mono-ligated complexes present an aryloxy-bridged dimeric structure, which is retained in solution in the case of Zn complexes but not with aluminum according to DOSY NMR experiments. Bis(ligated) Al and Zn complexes exhibit fluxional behaviour in solution attributed to coordination-decoordination of the amidine moiety and the rotation around the amidine C-NR' 2 and C-Ar bonds. These complexes were tested for the ROP of rac -lactide in solution and under bulk conditions. In both cases, the most performant catalysts are Zn complexes featuring a phenoxy-amidine ligand with a pendant additional dimethylamino arm.

Ethylene- and phenylene-bridged bis(salicylamidine) ligands have been readily prepared from ethylene or phenylenediamine and iminium chloride derivatives generated in situ from N , N -dialkylsalicylamides. The former, in its diprotonated form (FAlenH 2 ), reacts with AlMe 3 to afford a zwitterionic dimethyldiphenoxyaluminate complex with the FAlen ligand monoprotonated and in a bidentate κ 2 O , O' fashion. A phenylene-bridged proligand behaves differently, yielding a neutral methylaluminum complex bearing a κ 3 O , N , O' -coordinated FAlen ligand. From these complexes, methyl anion abstraction with B(C 6 F 5 ) 3 or a reaction with Schrock's alcohol leads to the corresponding aluminum cationic or alkoxy complexes in which a κ 4 O , N , N' , O' -coordination mode of the FAlen ligand is observed. X-ray diffraction studies of the proligands and of the complexes show that the amidine functions feature a trans configuration when the N -amidine atom is not coordinated to the metal and conversely a cis configuration when it is. Density functional theory calculations show that trans - cis isomerization of the amidine functions occurs upon coordination with the metal ion with very low energy barriers. They also confirm the intuition that the denticity of the FAlen ligands in the complexes is directly related to the electron richness of the metal ion. At last, FAlen Al complexes are used as initiators for the controlled ring-opening polymerization of rac -lactide to afford poly(lactic acid) with slight isotactic bias.

Aza-boron-dipyrromethenes (Aza-BODIPYs) are an increasingly studied class of fluorophores. They can be seen as an azadipyrromethene ("aza-DIPY") ligand rigidified by a metalloid, a boron atom. Based on this idea, a series of complexes of group 13 metals (aluminum and gallium) have been synthesized and characterized. The impact of the metal and of the nature of the substituents of aza-DIPY core were investigated. The photophysical and electrochemical properties were determined, and an X-ray structure of an azaGaDIPY was obtained. These data reveal that azaGaDIPY and azaAlDIPY exhibit significant red-shifted fluorescence compared to their analogue aza-BODIPY. Their emission can go up to 800 nm for the maximum emission length and up to NIR-II for the emission tail. This, associated with their electrochemical stability (no metal release whether oxidized or reduced) makes them a promising class of fluorophores for optical medical imaging. Moreover, X-ray structure and molecular modeling studies have shown that this redshift seems to be more due to the geometry around the boron/metal than to the nature of the metal.

A phosphine gold(I) and phosphine-phosphonium gold(I) complexes bearing a fluorescent coumarin moiety were synthesized and characterized. Both complexes displayed interesting photophysical properties: good molar absorption coefficient, good quantum yield of fluorescence, and ability to be tracked in vitro thanks to two-photon imaging. Their in vitro and in vivo biological properties were evaluated onto cancer cell lines both human and murine and into CT26 tumor-bearing BALB/c mice. They displayed moderate to strong antiproliferative properties and the phosphine-phosphonium gold(I) complex induced significant in vivo anti-cancer effect., (© 2022 Wiley-VCH GmbH.)

A family of gold(i)-phosphonium-phosphine complexes was synthesized thanks to an efficient 5-step strategy, which involves a phospha-Fries rearrangement. It enables the facile variation of the phosphonium moiety. All the complexes along with a synthetic intermediate were fully characterized (a crystal structure was obtained for two of them). The antiproliferative properties of the six novel complexes were evaluated on three human cancer cell lines (A549, MDA-MB-231, and SW480) and compared to those of three benchmark anticancer drugs used in clinics (oxaliplatin, 5-fluorouracil, and paclitaxel) and to a phosphonium-free gold(i) complex [Au(PPh 3 )Br]. All the gold(i) complexes, containing a phosphonium, displayed strong anti-proliferative properties. They were more efficient than oxaliplatin and 5-fluorouracil, and one of the complexes was even more efficient than paclitaxel.

We report the synthesis of a series of Zr and Ti complexes bearing phosphasalen which differs from salen by the incorporation of two P atoms in the ligand backbone. The reaction of phosphasalen proligands (1a-1c)H 2 with Zr(CH 2 Ph) 4 led to different products depending on the nature of the N,N-linker in the ligand. In the case of ethylene-linked phosphasalen, octahedral Zr complex 2a formed as a single stereoisomer in trans geometry. With the phenylene linker, it was shown by dynamic NMR spectroscopy that complex 2b exists as a mixture of trans and cis-β isomers in solution, both enantiomers (Δ and Λ) of the cis-β isomer being in fast equilibrium with respect to the NMR time-scale. The use of a propylene-linked phosphasalen proligand 1cH 2 led to a mixture of complexes among which a binuclear Zr complex 2c bridged only by one phosphasalen ligand could be isolated and characterized. Addition of 2 equiv. of i PrOH to 2a and 2b afforded diisoproxy Zr complexes 3a and 3b as a mixture of trans and cis-β isomers, the latter undergoing fast Δ/Λ isomerization in solution. Addition of B(C 6 F 5 ) 3 to 2a and 2b gave cationic monobenzyl Zr complexes 4a and 4b which have been further converted into cationic alkoxy Zr complexes 5a-b and 6a-b by alcoholysis with i PrOH and (S)-methyl-lactate, respectively. The reaction of the phosphasalen proligands with Ti(NMe 2 ) 4 proceeded diastereoselectively giving rise to Ti complexes 7a-c in octahedral geometry with cis-β wrapping of the ligand. The complexes have been tested for the ROP of rac-lactide. The neutral phosphasalen Ti and Zr complexes showed only poor activity probably due to the encumbered and electron donating nature of the phosphasalen ligand. In contrast, the cationic Zr alkoxides 5a, 6a and 6b are effective initiators for the controlled and hetero-selective ROP of rac-lactide.

The synthesis of o-boronato- and o-trifluoroborato-phosphonium salts supported by the L-amino acid side chain is described. The synthesis of these new class of amino acid derivatives was achieved by stereoselective quaternization of o-(pinacolato)boronatophenylphosphine with β- or γ-iodo amino acid derivatives which are prepared from L-serine or L-aspartic acid, respectively. The quaternization of the phosphine was performed using either iodo amino ester or carboxylic acid derivatives. In addition, free carboxylic acid and amine derivatives were obtained by saponification or HCl acidolysis of o-boronato-phosphonium amino esters, respectively. The usefulness of these compounds in peptide coupling was demonstrated by coupling an o-boronato-phosphonium amino ester with an aspartic acid moiety. When the o-boronato-phosphonium amino acid or dipeptide derivatives were mixed with fluoride, the corresponding o-trifluoroborated products were cleanly and rapidly obtained in high isolated yields. The hydrolysis of these compounds at room temperature using a phosphate buffer pH 7/CD3CN mixture has shown only traces of free fluoride F(-) after several days. Finally, a preliminary radiolabeling essay has proven the facile [(18)F]-fluoride incorporation and high stability of the radiolabeled product in aqueous conditions. Indeed, this new class of boron-phosphonium amino acid derivatives shows promising properties for their applications in synthesis and labeling of peptides.

An efficient synthesis of boronated phosphines with an o-phenylene-bridge prepared from sec-phosphine boranes and using benzyne chemistry is reported. Successive reactions of sec-phosphine boranes with n-BuLi and 1,2-dibromobenzene, and then with boron reagents, afford the o-boronatophenylphosphine derivatives in 71% yields. The use of P-chirogenic sec-phosphine boranes leads to the free boronated phosphines with retention of configuration at the P-center after decomplexation. The reaction of P-chirogenic o-boronatophenylphosphine with KHF2 affords the corresponding trifluoroborated phosphine with ee >98%.