This article reviews our contribution in the field of radical synthetic chemistry, focusing on cascades relying on the use of propargylic BMDMS ethers and asymmetric synthesis using enantiopure vinylsulfoxides. THE 5-EXO-DIG CYCLIZATION OF BMDMS PROPARGYLIC ETHERS: AN EFFICIENT TRIGGER FOR RADICAL CASCADES The vinyl radical, a precious tool The vinyl radical of type 3 resulting from the highly ...

The spirastrellolides are a novel family of structurally unprecedented marine macrolides which show promising anticancer properties due to their potent inhibition of protein phosphatase 2A. In the preceding paper, a modular strategy for the synthesis of spirastellolide A methyl ester which allowed for the initial stereochemical uncertainties was outlined, together with the synthesis of a series...

Antimony is one of the constituents of pewter, an alloy composed of a minimum of 90% tin with the balance being made up with copper, antimony and perhaps some bismuth. A method has been developed to determine Sb in acetic acid leachates from pewter cups. The employed instrumentation, an atomic absorption spectrometer, equipped with a quartz trap-and-atomizer device, is simple and relatively ine...

Since its discovery the rearrangement of R-metalated ethers, particularly the [2,3]-Wittig rearrangement, has been the subject of intensive mechanistic and synthetic investigations.1 Relative to the [2,3]-shift, the [1,2]-Wittig rearrangement has received relatively little publicity. Most studies of the [1,2]-Wittig have been mechanistic in origin, resulting in the widely accepted theory that t...

A three-component coupling of vinyl triflates and boronic acids to alkenes catalyzed by palladium is reported. Using 1,3-dienes, selective 1,2-alkene difunctionalization is observed, whereas the use of terminal alkenes results in 1,1-alkene difunctionalization. The reaction outcome is attributed to the formation of stabilized, cationic Pdπ-allyl intermediates to regulate β-hydride elimination. ...

The photostimulated reaction of Me3Sn ion with mono, di and trichloro arenes in liquid ammonia gave very good yields of stannanes by the SRN1 mechanism. These products reacted by a palladium-catalized cross coupling reaction with halobenzenes to give phenylated products also in very goods yields. Similar yields can be obtained in one-pot reactions. Introduction The radical nucleophilic substitu...

A highly convergent, stereocontrolled total synthesis of the potent antiproliferative agent (+)phorboxazole A (1) has been achieved. Highlights of the synthesis include: modified Petasis-Ferrier rearrangements for assembly of both the C(11-15) and C(22-26) cis-tetrahydropyran rings; extension of the Julia olefination to the synthesis of enol ethers; the design, synthesis, and application of a n...

The archazolids are a family of unsaturated polyketides with low nanomolar inhibitory activity and excellent selectivity against mammalian V-ATPases (Scheme 1).1 The isolation of archazolids A (1) and B (2) from the myxobacterium Archangium gephyra and the constitutions of these natural products were reported by Höfle et al. several years ago.2 In 2006, Menche and co-workers disclosed the relat...