Ketones, diallyl carbonylation

The reactions of allyliron tricarbonyl halides with donor molecules were studied. Triphenylphosphine substituted only one carbonyl, that trans-oriented with respect to the halogen of the form (XIX) [432). The phosphine derivatives of (XX) were not isolated as pure compounds. The complexes were decomposed entirely by dimethyl sulfoxide, giving [(0113)280] jFeX2 [435). Thermal decomposition of C3H5Fe(CO)3X depended on the medium and gave either diallyl, or diallyl ketone, together with propene, allyl ether, Fe(CO)5, and FeX2 [436). 

A,A-Disubstituted amides can be converted to alkynyl ketones by treatment with alkynylboranes RCONR2 + (R C=C)3B RCOC=CR. Lactams react with triallylborane to give cyclic 2,2-diallyl amines after treatment with methanol, and then aqueous hydroxide. Triallylborane reacts with the carbonyl group of lactams, and after treatment with methanol and then aqueous NaOH gives the... 

Asymmetric hydrogenation of either a carbonyl or an imino group to a hydroxyl group or an amino group has frequently been employed for the introduction of chirality in amino acid syntheses. Corey s catecolborane-oxazaborolidine protocol enables transformation of difluoromethyl ketone 1 into alcohol 2 with excellent enantioselectivity. The reaction of diastereoselective amination of a-hydroxyaldehyde 3 with A,A-diallylamine and 2-furyl-boronic acid provides furyl amino alcohol 4 in good chemical yield along with excellent diastereoselectivity. This protocol is applicable for the preparation of amino acids and amino alcohols with a trifluoromethyl group by the combination of /V,/V-diallyl or N,N-dibenzyl amine and aromatic, heteroaromatic and alkenyl boronic acids [7]. The usual chemical transformations as shown in steps 5 to 8 in Scheme 9.1 lead to (2S,3R) difluorothreonine 5 [8]. 

The dichloro-dodecatriene-ruthenium complex is a highly efficient catalyst for the one-pot internal redox process that converts allylic alcohols (RC=C-C(OH) into carbonyl compoimds (RC-C-C=0, ketones or aldehydes) in the presence of CSCO3 imder N2 with high yields and turnover frequencies (TOP) in THF or H2O [Cadiemo et al. Chem Commun 232 2004, see also van der Drift et al. J Organomet Chem 650 1 2002]. It is also an efficient catalyst for the de-protection of V-allylic and V-diallylic substrates (with 3mol% of Ru) in aqneons solntion at... 

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