Max Malacria - Selected Publications#

1) The behavior of 1, n-enynes in the presence of transition metals
C Aubert, O Buisine, M Malacria
Chemical reviews 2002, 102, 813-834.

We illustrated at this time that the use of transition-metal catalysts to promote the cyclization of 1,n-enynes was exponentially growing. As it clearly appeared in this review, cyclizations catalyzed by palladium complexes constitute the largest part of the accomplishments to date. However,the use of metal species other than Pd has really increased, and new types of reactions and processes have emerged. Indeed, the cyclizations of 1,n-enynes have been achieved either in a catalytic or stoichiometric manner and represent a versatile and powerful approach to a large variety of products by simple manipulation of the catalyst and by proper choice of the substrate. These cyclizations which mostly generate 1,3- or 1,4- dienes enhance the ability to construct polycyclic compounds in a highly atom economical approach by combining with Diels-Alder or coupling reactions or
polycyclizations. Thus, numerous applications in the field of natural product synthesis have been reported.

2) The Effect of a Hydroxy Protecting Group on the PtCl2‐Catalyzed Cyclization of Dienynes—A Novel, Efficient, and Selective Synthesis of Carbocycles
E Mainetti, V Mouriès, L Fensterbank, M Malacria, J Marco‐Contelles
Angewandte Chemie International Edition 2002, 41 (12), 2132-2135

We have shown that PtCl2-catalyzed cyclizations of dienyne systems with a hydroxy group at the propargylic position can be chemo-, regio-, and stereocontrolled by tuning the nature of the protecting group at this position. With a free hydroxy group or the corresponding ethers, the previously unknown tetracyclo[,308,10]]decane skeleton was obtained diastereoselectively. An O-acyl protecting group completely shifted the reaction towards apreviously undescribed rearrangement, which afforded bicyclic enolesters with a fused cyclopropane ring in , position that were methanolyzed to versatile [n.1.0]]bicylic ketones as
single diastereomers. This combined two-steps protocol can be regarded as an equivalent of the well-known cycloisomerization
of unsaturated -diazocarbonyl compounds with obvious advantages.

3) Efficient preparation of functionalized hybrid organic/inorganic Wells− Dawson-type polyoxotungstates
S Bareyt, S Piligkos, B Hasenknopf, P Gouzerh, E Lacôte, S Thorimbert, M Malacria
Journal of the American Chemical Society 2005, 127 , 6788-6794

We have devised efficient methods to prepare tin-substituted R2- and R1-Wells-Dawson polyoxotungstates using a high-yielding phase transfer procedure. Those complexeswere not previously known in the R1 series. We then were able to cleanly attach amines or alcohols to the side chains. Thisallowed us to access a variety of new structures, which could be used for several applications in biology and material science.

4) Visible‐light‐induced photoreductive generation of radicals from epoxides and aziridines
MH Larraufie, R Pellet, L Fensterbank, JP Goddard, E Lacôte, M Malacria, C.Ollivier
Angewandte Chemie International Edition 2011, 50 , 4463-4466

We have extended the scope of visible-light photoredox catalysis to the generation of radicals from epoxides and aziridines. Then, we took advantage of the reactivity of the photogenerated radical to create new carbon–carbon bonds through a highly diastereoselective radical ring-opening/allylation tandem process.

5) Platinum dichloride-catalyzed cycloisomerization of ene-ynamides
F Marion, J Coulomb, C Courillon, L Fensterbank, M Malacria
Organic letters 2004, 6, 1509-1511

We reported the first use of eneynamides as versatile partners for PtCl2-catalyzed cycloisomerization reactions. Various ene-tosylynamides react with platinum(II) chloride and lead to bicyclic nitrogenated heterocycles. This unprecedented and easily
operated process can be coupled with a hydrolysis of the intermediate cyclic tosylenamides in a one-pot transformation, which provides cyclobutanones.

6) Cobalt-catalyzed cyclotrimerization of alkynes: the answer to the puzzle of parallel reaction pathways
N Agenet, V Gandon, KPC Vollhardt, M Malacria, C Aubert
Journal of the American Chemical Society 2007 129 , 8860-8871

We have shown that the key intermediate in all cases of cyclotrimerization of alkynes is a triplet cobaltacyclopentadiene obtained by oxidative coupling of the corresponding CpCo(bisalkyne) complex and subsequent spin change via a minimum energy crossingpoint (MECP). From that species, two different catalytic cycles lead to an arene product, depending on the nature of the alkyne and other ligands present: either alkyne ligation to furnish a cobaltacyclopentadiene-(alkyne) intermediate or trapping by a ó-donor ligand to generate a coordinatively saturated cobaltacyclopentadiene(PR3) complex. The former leads to the CpCo-complexed arene product via intramolecular cobaltassisted[4 + 2]] cycloaddition, whereas the latter may in the case of a reactive dienophile (butynedioicacid), undergo direct intermolecular [4 + 2]] cycloaddition to generate a cobaltanorbornene. The bridgeheadcobalt atom is then reductively eliminated after another change in spin state from singlet to triplet.

7) Gold (I)‐and gold (III)‐catalyzed cycloisomerization of allenynes: a remarkable halide effect
G Lemière, V Gandon, N Agenet, JP Goddard, A de Kozak, C Aubert, L Fensterbank, M Malacria
Angewandte Chemie 2006 ,45, 7596-7599.

Chloride plays a crucial role in the gold-catalyzed cycloisomerization of allenyne precursors and allows the completely selective formation of a hydrindiene vs. the usual Alder-ene product. This effect could be rationalized computational studies that shed a new light on the electrophilic metal-catalyzed cycloisomerization of polyunsaturated systems.

8) From PtCl2‐and Acid‐Catalyzed to Uncatalyzed Cycloisomerization of 2‐Propargyl Anilines: Access to Functionalized Indoles
K Cariou, B Ronan, S Mignani, L Fensterbank, M Malacria
Angewandte Chemie International Edition 2007, 46, 1881-1884

We have devised an expedient route to 2,3-functionalized indoles and notably 3-alkoxyindoles, whichrelies on the use of PtCl2 or proton catalysis. The mostintriguing aspect of this process is that the tuning ofsubstituents on the nitrogen atom, as well as reaction conditions, notably temperature, allows an easy and versatileaccess to a myriad of indole substrates.

9) Highly Efficient Peptide Bond Formation to Functionalized Wells‐Dawson‐Type Polyoxotungstates
S Bareyt, S Piligkos, B Hasenknopf, P Gouzerh, E Lacôte, S Thorimbert, M Malacria
Angewandte Chemie International Edition 2003 ,42 , 3404-3406.

We have demonstrated that we could prepare both [a1-P2W17O61{Sn(CH2)2CO2H}]]7 and [a2-
P2W17O61{Sn(CH2)2CO2H}]]7, and also further make derivatives of the a2 series by attaching organic molecules to the arm.
Very efficient peptide bond formation is then possible using Wells-Dawson POM.

10) Chiral recognition of hybrid metal oxide by peptides
K Micoine, B Hasenknopf, S Thorimbert, E Lacôte, M Malacria
Angewandte Chemie International Edition 2009, 48, 3466-3468

We have shown that molecular recognition of the chiral metal oxide surface of an a1-substituted Dawson polyoxotungstate enabled its kinetic resolution—atool from organic chemistry—, which has been made possibleby the unique properties of organic hybrids of POMs. This finding opens new ways to applications of designed chiralhybrids in catalysis (chiral anions), medicinalchemistry(POMs have numerous biological properties), and materials science.

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