Fluoride-Catalyzed Cross-Coupling of Silylamides to CF-Acrylates: Access to Highly Functionalized Trifluoromethylated and Quaternary Fluorinated Molecular Architectures.

A direct and simple catalytic coupling of nonfluorinated and fluorinated silylbutenamides with β-CF α,β-unsaturated esters mediated by fluoride ion was carried out. The transformation proceeded with excellent yields to afford new, highly functionalized trifluoromethylated and quaternary fluorinated products.

Iridium(III) Catalyzed -Selective Allylic Arylation of α-Fluoro But-1-enoic Acid Amides via β-F-Elimination in Water.

Allylic arylation of α-fluoro but-1-enoic acid amides with arylboronic acids was carried out in water by comparing the catalytic activity of iridium(III) and rhodium(III). Ir(III) has shown a strong superiority over Rh(III) to give allyl-aryl coupling products with excellent stereoselectivity in favor of the -isomer. The origin of high stereoselectivity is perhaps because of the a coordination of iridium Ir-N or Ir-O.

Rhodium(III) Catalyzed Regioselective and Stereospecific Allylic Arylation in Water by β-Fluorine Elimination of the Allylic Fluoride: Toward the Synthesis of Z-Alkenyl-Unsaturated Amides.

A direct coupling of arylboronic acids with allylic fluorides was carried out in water without additives using a rhodium(III) catalyst (Cp*RhCl). The transformation proceeded with excellent γ-selectivity to afford major allyl-aryl coupling products () γ-substituted α,β-unsaturated amides. The reactions of α-chiral allylic fluorides took place with excellent α-to-γ chirality transfer to give allylated arenes with a stereogenic center at the benzylic and allylic position.

A theoretical study of the diastereoselective allylation of aldehydes with new chiral allylsilanes.

In this paper, we investigate the reaction mechanism for the synthesis of new functionalized chiral hydroxyamides theoretically, using a concerted density functional theory (DFT)-conceptual DFT-quantum theory of atoms-in-molecules (QTAIM) approach, which casts light on the main physicochemical properties responsible for the observed selectivity. We use a particular nucleophilic addition step to illustrate the strengths of this general strategy, which could, in principle, be applied to unravel the main features of any chemical synthesis.

1,4 Addition of unprotected pyrrole onto chiral acrylamides: toward synthesis of new polypeptidic architectures.

A diversity of new functionalized acyclic chiral pyrroloamide compounds were synthesized by a simple and robust process involving the creation of a C-C bond between unprotected pyrroles and acyclic chiral acrylamides using Lewis acids. This alkylation reaction using Michael acceptors has been optimized, allowing us to obtain channel selective access to monoalkylated or dialkylated pyrroles, in good yields. Di- and tripeptide deriving acrylamides have also been used as the reaction partner.

Formal synthesis of dictyostatin and synthesis of two dictyostatin analogues.

A formal convergent synthesis of dictyostatin from (R)-Roche ester is described. Synthetic highlights include a Ni-catalyzed Nozaki-Hiyama-Kishi coupling between an aldehyde and a Z vinyl iodide to assemble the two main fragments, a diastereoselective Myers alkylation, a stereoselective Evans aldolization, two asymmetric Duthaler crotyltitanations, and a stereoselective Pd-catalyzed Marshall allenylindium addition to install the stereogenic centers of dictyostatin. The synthesis of (9R)-epi-dictyostatin and a new ring-contracted dictyostatin isomer were also achieved.

Acryloyl chloride: an excellent substrate for cross-metathesis. a one-pot sequence for the synthesis of substituted alpha,beta-unsaturated carbonyl derivatives.

A diverse set of functionalized alpha,beta-unsaturated carbonyl compounds were synthesized in good yield by utilizing a very simple one-pot process involving a cross-metathesis between acryloyl chloride and a terminal olefin followed by the addition of a nucleophile.

Synthetic efforts toward the macrolactone core of Leucascandrolide A.

A chemoselective synthesis of 1, the macrocyclic core of leucascandrolide A, has been achieved by utilizing highly enantioselective allylmetalations, an enantioselective Noyori reduction of a propargylic ketone, and olefin metatheses as the key steps.

Ruthenium-catalyzed cross-metathesis between diallylsilanes and electron-deficient olefins.

Diallysilanes can be selectively coupled with electron-deficient olefins under cross-metathesis (CM) conditions using the Hoveyda-Grubbs catalyst to produce mono- and/or bis-CM compounds in good yield. The formation of the mono- and the bis-CM compounds depends on the nature of the electron-deficient olefin.

Tetrafibricin: synthesis of the C1-C13, C15-C25, and C27-C40 fragments.

[structure: see text] A sequence of chemoselective cross-metathesis reactions and enantioselective allyltitanations of aldehydes has been used to prepare the C1-C13, C15-C26, and C27-C40 fragments of tetrafibricin.

Regioselective cross-metathesis reaction induced by steric hindrance.

[reaction: see text] When hexa-1,5-dien-3-ol is protected with bulky groups, a regioselective cross-metathesis reaction can take place at the C5-C6 double bond.

Stereoselective synthesis of the C1-C13 fragment of (+)-discodermolide using asymmetric allyltitanations.

[reaction: see text] The synthesis of the C1-C13 fragment of (+)-discodermolide has been achieved. The configurations of the stereogenic centers have been controlled by enantioselective allyl- and crotyltitanations of aldehydes, and the Z configuration of the olefin at C8-C9 was controlled by a ring-closing metathesis.

Total synthesis of (+)-strictifolione.

[reaction: see text] The synthesis of (+)-strictifolione was achieved from 3-phenylproprionaldehyde by using enantioselective allyltitanations to control the stereogenic centers at C6, C4', and C6' and a cross-methathesis to control the configuration of the double bond at C1'-C2'.

Tandem cross-metathesis/hydrogenation/cyclization reactions by using compatible catalysts.

[reaction: see text] A one-pot tandem cross-metathesis/hydrogenation/cyclization procedure was achieved at room temperature, under 1 atm of hydrogen, in the presence of a ruthenium catalyst and PtO(2) showing the compatibility of the two catalysts. This tandem reaction allows the synthesis of substituted lactones and lactols from acrylic acid and acrolein, respectively, in the presence of unsaturated alcohols.

Enantioselective allyltitanations and metathesis reactions. Application to the synthesis of piperidine alkaloids (+)-sedamine and (-)-prosophylline.

An enantioselective synthesis of the piperidine alkaloids (+)-sedamine and (-)-prosophylline is reported. The synthesis of (+)-sedamine has been achieved in 12 steps with an overall yield of 20% from benzaldehyde, and (-)-prosophylline was obtained in 15 steps with an overall yield of 9.2%, starting from D-glyceraldehyde acetonide 14.