Kumada–Tamao–Corriu Coupling of Heteroaromatic Chlorides and Aryl Ethers Catalyzed by (IPr)Ni(allyl)Cl

The complex (IPr)Ni(allyl)Cl (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolidene) catalyzes the cross-coupling reactions of heteroaromatic chlorides with aryl Grignard reagents. Catalyst loadings as low as 0.1 mol % have been used to afford the products in excellent yields. This nickel-based catalytic system also promotes the activation of the C_Ar–O bond of anisoles in the Kumada–Tamao–Corriu reaction under fairly mild conditions

Directed <i>Ortho</i>-Lithiation of Aminophosphazenes: An Efficient Route to the Stereoselective Synthesis of <i>P</i>‑Chiral Compounds

<i>Ortho</i>-directed lithiation of <i>P</i>,<i>P</i>-diphenylaminophosphazenes followed by electrophilic quench is described as an efficient process for synthesizing <i>P</i>-chiral <i>ortho</i>-functionalized derivatives in high yields and diastereoselectivities. The method allows the tunable preparation of structurally diverse enantiopure <i>P</i>-chiral compounds including phosphinic and phosphinothioic amides, phosphinic esters, phosphine oxides, and <i>o</i>-aminophosphines

Synthesis of P‑Stereogenic Benzoazaphosphole 1‑Oxides via Alkynylation of P‑Stereogenic ortho-Aurated and ortho-Iodo Phosphinic Amides

An efficient methodology for the synthesis of P-stereogenic dihydrobenzoazaphosphole 1-oxides via intramolecular 5-<i>exo</i>-dig alkyne hydroamination promoted by tetrabutylammonium fluoride is herein described. The required chiral <i>o</i>-alkynylphosphinic amide starting materials were prepared in high yields under very mild reaction conditions through alkynylation of P-stereogenic (O^C)-cyclometalated (phosphinic amide)­dichlorogold­(III) complexes and Sonogashira cross-coupling of ortho-iodo P-stereogenic phosphinic amide

Synthesis of P‑Stereogenic Benzoazaphosphole 1‑Oxides via Alkynylation of P‑Stereogenic ortho-Aurated and ortho-Iodo Phosphinic Amides

An efficient methodology for the synthesis of P-stereogenic dihydrobenzoazaphosphole 1-oxides via intramolecular 5-<i>exo</i>-dig alkyne hydroamination promoted by tetrabutylammonium fluoride is herein described. The required chiral <i>o</i>-alkynylphosphinic amide starting materials were prepared in high yields under very mild reaction conditions through alkynylation of P-stereogenic (O^C)-cyclometalated (phosphinic amide)­dichlorogold­(III) complexes and Sonogashira cross-coupling of ortho-iodo P-stereogenic phosphinic amide

Synthesis of P‑Stereogenic Benzoazaphosphole 1‑Oxides via Alkynylation of P‑Stereogenic ortho-Aurated and ortho-Iodo Phosphinic Amides

An efficient methodology for the synthesis of P-stereogenic dihydrobenzoazaphosphole 1-oxides via intramolecular 5-<i>exo</i>-dig alkyne hydroamination promoted by tetrabutylammonium fluoride is herein described. The required chiral <i>o</i>-alkynylphosphinic amide starting materials were prepared in high yields under very mild reaction conditions through alkynylation of P-stereogenic (O^C)-cyclometalated (phosphinic amide)­dichlorogold­(III) complexes and Sonogashira cross-coupling of ortho-iodo P-stereogenic phosphinic amide

Cycloaurated Phosphinothioic Amide Complex as a Precursor of Gold(I) Nanoparticles: Efficient Catalysts for A³ Synthesis of Propargylamines under Solvent-Free Conditions

A C,S-cycloaurated complex based on an ortho-substituted phosphinothioic amide framework has been synthesized in high yield through tin­(IV)–Au­(III) transmetalation from the corresponding chlorodimethylstannyl derivative. The latter was prepared in a two-step process involving directed ortho lithiation/quenching with Me₃SnCl followed by Me/Cl exchange. The tin­(IV) and gold­(III) complexes have been characterized in solution and in the solid state. In both complexes, the phosphinothioic amide moiety acts as a C–C–P–S pincer ligand with formation of five-membered-ring metalacycles. The use of the gold­(III) complex in the amine–aldehyde–alkyne (A³) three-component coupling synthesis of propargylamines showed that the compound is transformed into the Sonogashira-type <i>o</i>-alkynylphosphinothioic amide with generation of Au­(I) nanoparticles with an average size of around 7 nm. These nanoparticles proved to be excellent catalysts in A³ coupling processes, providing propargylamines in high yields under solvent-free conditions with loadings as low as 0.1 mol % and without the use of additives

Phyllanthus emblica

The experimentally observed stereomutation of spiro-1,2-oxaphosphetanes is shown by DFT calculations to proceed through successive M_B2 or M_B4 and M_B3 mechanisms involving two, four, and three Berry pseudorotations at phosphorus, respectively. Oxaphosphetane decomposition takes place in a single step via a polar transition state. The calculated activation parameters for this reaction are in good agreement with those determined experimentally