Intramolecular endo-dig hydrosilylation catalyzed by ruthenium: evidence for a new mechanistic pathway

The ruthenium catalyst [Cp*Ru(MeCN)3]PF6 effects a novel intramolecular hydrosilylation of homo- and bis-homopropargylic alcohols, producing products of unique regioselectivity under very mild conditions with excellent selectivity. The reaction is compatible with a wide range of functional groups and tolerates substantial steric bulk. In addition to producing valuable synthetic intermediates thus far obtainable only in circuitous fashion, the results imply the necessity for a reexamination of the mechanism surrounding trans-hydrosilylation reactions, at least for ruthenium catalysts. At the very least, a simple cis addition/isomerization mechanism almost certainly cannot be active in this case. A silicon-ruthenium transposition could potentially provide a rationalization. However, the evidence for any products of syn addition with nonhydrido ruthenium catalysts is very scarce. Alternatively, a direct trans addition to orthogonal p-systems is also a possibility.     

A Ru-catalyzed tandem alkyne-enone coupling/Michael addition: synthesis of 4-methylene-2,6-cis-tetrahydropyrans

[reaction: see text] A Ru-catalyzed tandem alkyne-enone coupling/Michael addition reaction is reported. It provides an efficient, atom-economic entry to 4-methylene-2,6-cis-tetrahydropyrans from simple, readily available homopropargylic alcohols and beta,gamma-unsaturated enones in good yields. Further functionalization of the resultant vinylsilane leads to the synthesis of either geometrically defined trisubstituted alkene exocyclic to the 2,6-cis-dihydropyran.     

On the regioselectivity of the Ru-catalyzed intramolecular [5 + 2] cycloaddition

The influence of substituents on which cyclopropyl bond cleaves in the cycloisomerization of cyclopropylenynes catalyzed by CpRu(N&tbd1;CCH(3))(3)(+)PF(6)(-) is compared to the corresponding Rh-catalyzed reaction. With the trans cyclopropyl substrates, the bond energy of the cleaving bond appears to be an important factor. With cis cyclopropyl substrates, steric effects appear to dominate.     

Measurement ofR ine + e − annihilation for\sqrt s between 7.4 and 9.4 GeV

The rationR=σ(e ⁺ e ^?→hadrons)/σ(e ⁺ e ^?→ µ⁺ µ^?) was measured with the LENA detector at DORIS in a scan between 7.40 and 7.48 GeV and between 8.67 and 9.43 GeV center of mass energies. Corrected for QED radiative effects,R is found to be constant with an average value ofR=3.37 ±0.06_stat±0.23_syst. No narrow resonances withΓ _ee (Γ _had/Γ _tot)?0.30 keV (95% C.L.) and no steps have been observed. Based on this value ofR, revised values for υ(1S) resonance parameters are presented.     

A new approach to sulfenylated enolates

Bissulfenylation followed by monodesulfenylation with a Grignard reagent cleanly provides magnesium enolates of α-phenylthiocarbonyl compounds for aldol condensation.     

Stereocontrolled synthesis of (+)-boronolide

Boronolide was synthesized stereoselectively from hydroxyacetylfuran 5 and valeraldehyde 6 using a novel dizinc aldol catalyst. Ring closing metathesis provides the lactone ring. The synthesis requires 12 steps and proceeds in 26% overall yield. [reaction: see text]