3 undecane-4,7,11 trione

Recently, a first example of an organocatalytic asymmetric domino Knoevenagel/ Diels-Alder reaction was reported by Barbas and coworkers (Scheme 2.182) [409]. Spiro[5,5]undecane-l,5,9-triones of type 2-818/2-819 were obtained from comma-daily available 4-substituted-3-butene-2-ones 2-813, aldehydes 2-814, and Mel-drum s acid (2-801) in the presence of 20 mol% of the amino acid 2-815 with 80-95% ee and diastereoselectivity of dr> 12 1. 

Tu and co-workers [189] described a series of new 3-pyrimidin-5-ylpropanamides 140, spiro[5.5] undecane-1,5,9-triones 141 and pyrimidin-5-ylpropanoic acids 142... 

Treatment of a benzene suspension of the copper(II) complex of heptane-2,4,6-trione (htHj) with phosgene gives a cyclic organic product [193a] the analogous copper(II) complexes of nonane-3,5,7-trione (ntHj) and undecane-4,6,8-trione (udtHj) give a similar product [1298] ... 

SCHEME 2.23 Asymmetric synthesis of spiro[5,5]undecane-l,5,9-trione derivatives 87. 

D. B. Ramachary, N. S. Chowdari, C. F. Barhas IB, Angew. Chem. Int. Ed. Engl. 2003, 42, 4233 237. Organocatalytic asymmetric domino Knoevenagel/Diels-Alder reactions a hioorganic approach to the diastereospecific and enanti-oselective construction of highly suhstituted spiro[5,5] undecane-1,5,9-triones. 

D. B. Ramachary, Y. V. Reddy, A. Baneijee, S. Baneqee, Org. Biomol. Chem. 2011, 9, 7282-7286. Design, synthesis and biological evaluation of optically pure functionalized spiro[5,5]undecane-l,5,9-triones as HIV-1 inhibitors. 

C2iH2205f 7,11 Bis(5-methy1-2-fury1)spiro[5.5]undecane-1,5,9-trione, 45B, 352... 

Hydroformylation of PhCH=CHMe in the presence of RhCl(PPh3)3 produces PhCH(CHO)-CHa-CH3 and PhCH3-CH(CHO)-CH3, as well as some PhCH2 CH2 CH3. Both Rh4(CO)i2 and mixed carbonyl-phosphine complexes derived from Rh4(CO)i2 and from Rh,(CO)ie are active catalysts for hydroformylation of alkenes. Acyl-rhodium intermediates may be important when Rh4(COX2 is the catalyst, for [Rh-(C0)2(02CR)]2 dimers have been isolated from alkene hydroformylations in which this polynuclear carbonyl has been the catalyst. Rh4(CO)i2 also catalyses the reaction between ethylene and carbon monoxide, which produces several products, including octane-3,6-dione, undecane-3,6,9-trione, and tetradecane-3,6,9,12-tetraone. The products obtained indicate a mechanism in which addition of ethylene to rhodium and insertion of carbon monoxide into a rhodium-carbon bond alternate. ... 

On another occasion, Barbas s group developed the first organocatalytic diastereospecific and enantioselective direct asymmettic domino Knoevenagel/ Diels-Alder reactions that produce highly substituted spiro[5,5]undecane-l,5,9-triones 57 from commercially available 54, aldehydes 55, and 2,2-dimethyl-l,3-dioxane-4,6-dione 56 (Scheme 1.16) [18]. Among the catalysts screened, 5,5-dimethyl thiazolidinium-4-carboxylate (DMTC) proved to be the optimal catalyst with respect to yield, and provided 57 in 88% yield and 86% ee. Up to 93% yield and 99% ee were observed when the reaction was extended to other substrates. It is noteworthy that the product 57 was accompanied by a trace amount of the unexpected symmetric spirocyclic ketone 58. 

The asymmetric domino three-component Knoevenagel/Diels-Alder addition reaction promoted by the primary amine catalyst 9-amino-9-deoxy-epi-quinine was also reported. Various pharmacological multisubstituted spiro[5,5]undecane-1,5,9-triones were obtained in moderate to good yields (up to 81%) with excellent diastereo-(>99 1 dr) and enantioselectivities (up to 97% ee) [19]. The enamine-mediated Diels-Alder reactions of a,P-unsaturated ketones were also extended to nitroalkenes [20] and 3-olefmic oxindoles [21]. 

---