Unexpected rapid -stereomutation of phosphine oxides catalysed by chlorophosphonium salts.

-Stereomutation of phosphine oxides is extremely slow. We show that it is catalysed by chlorophosphonium salts (CPS) which can directly be formed in the system . The racemization of phosphine oxides at ambient conditions catalysed by 1 mol% of CPS takes 1-2 hours and can be arrested by additon of a primary alcohol.

Cellulitis and bacteraemia caused by Streptococcus dysgalactiae post radical vulvectomy and bilateral inguinal lymph node dissection for FIGO IB squamous cell carcinoma of the vulva, a case report.

Background: Streptococcus dysgalactiae, also known as Group C/G Streptococci, causes infection to humans and animals. Infectious syndromes range from mild pharyngitis and cellulitis, to bacteraemia and life-threatening sepsis. This report uniquely presents a case of Streptococcus dysgalactiae subspecies dysgalactiae causing fulminant sepsis post-radical vulvectomy.

Asymmetric addition of Grignard reagents to ketones: culmination of the ligand-mediated methodology allows modular construction of chiral tertiary alcohols.

A new class of biaryl chiral ligands derived from 1,2-diaminocyclohexane (1,2-DACH) has been designed to enable the asymmetric addition of aliphatic and, for the first time, aromatic Grignard reagents to ketones for the preparation of highly enantioenriched tertiary alcohols (up to 95% ee). The newly developed ligands L12 and L12' together with the previously reported L0 and L0' define a set of complementary chiral promoters, which provides access to the modular construction of a broad range of structurally diverse non-racemic tertiary alcohols, bearing challenging quaternary stereocenters. The present advancements bring to completion our asymmetric Grignard methodology by expanding the scope to aromatic organomagnesium reagents, while facilitating its implementation in organic synthesis thanks to improved synthetic routes for the straightforward access to the chiral ligands.

Wittig Olefination Using Phosphonium Ion-Pair Reagents Incorporating an Endogenous Base.

Despite common perception, the use of strong bases in Wittig chemistry is utterly unnecessary: we report a series of novel ion-pair phosphonium carboxylate reagents which are essentially "storable ylides". These reagents are straightforwardly prepared in excellent yields, and their fluxional nature permits clean olefination of a broad range of aldehydes and even hemiacetals.

Harnessing the Power of the Asymmetric Grignard Synthesis of Tertiary Alcohols: Ligand Development and Improved Scope Exemplified by One-Step Gossonorol Synthesis.

A series of -substituted cyclohexyldiaminophenolic ligands for the asymmetric Grignard synthesis of tertiary alcohols is reported. The 2,5-dimethylpyrrole-decorated ligand led to improved enantioselectivities and broadened the scope of the methodology. As an exemplar, we report an unprecedented highly selective one-step synthesis of gossonorol in 93% , also constituting the shortest formal syntheses of natural products boivinianin B and yingzhaosu C.