Construction of <i>cis</i>- and <i>trans</i>-Decahydroisoquinolines via Heterogeneous Catalytic Hydrogenation

MaGee, David I.; Lee, May Ling; Decken, Andreas

doi:10.1021/jo982055d

Cited by 14 publications

(4 citation statements)

References 22 publications

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“…Contrarily, when the steric repulsion dominates, hydrogenation occurs from the side opposite the substituent, leading to the cis − cis diastereomer. Similar studies correlating various functional groups with their ability to influence the adsorption of olefinic substrates in hydrogenation reactions on noble metal catalysts have been conducted by Thompson et al − and more recently by MaGee et al In their studies, Thompson and co-workers found that some functional groups had a strong affinity (also termed as haptophilicity) for the catalyst, resulting in hydrogenation products with a configuration opposite of that expected when considering only steric repulsion of the functional group. While their study was conducted on the hydrogenation of olefinic substrates over platinum- and palladium-based catalysts, our study was conducted on the hydrogenation of aromatic substrates over rhodium-based catalysts.…”

Section: Discussionsupporting

confidence: 53%

Functional-Group-Directed Diastereoselective Hydrogenation of Aromatic Compounds. 1

1999

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Diastereoselective liquid phase hydrogenation of a series of monosubstituted indane and tetralin substrates was studied on supported rhodium catalysts. Predominantly the cis-cis diastereomer, obtained by hydrogenation from the diastereoface opposite the substituent (at the stereogenic center), and the cis-trans diastereomer, obtained by hydrogenation from the diastereoface on the same side as the substituent, were formed. The diastereoselectivity between the two isomers was dependent on the steric repulsion or the electronic attraction of the substituent with the surface of the catalyst. The hydroxyl group did not exhibit a strong attraction (haptophilicity), and the cis-cis diastereomer was obtained as the major product. The amino group exhibited a very high haptophilicity, yielding primarily the cis-trans diastereomer. The diastereoselectivity obtained in the hydrogenation of all the substrates was influenced on addition of bases to the reaction mixture. In the case of alcoholic substrates, the selectivity to the cis-trans diastereomer could be substantially increased with alkaline hydroxide additives.

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Section: Discussionsupporting

confidence: 53%

Functional-Group-Directed Diastereoselective Hydrogenation of Aromatic Compounds. 1

1999

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“…It has been known for a long time that polar groups, especially hydroxyl groups, can influence stereochemical outcome of olefin hydrogenation over metals, particularly in rigid systems . To assess this assumption, diol 21 was prepared by acid-catalyzed hydrolysis of 20 and then subjected to hydrogenation over Pd/C.…”

Section: Resultsmentioning

confidence: 99%

Toward the Total Synthesis of Vinigrol: Synthesis of epi-C-8-Dihydrovinigrol

et al. 2009

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Two approaches to vinigrol starting from the advanced tricyclic core 7 have been explored using as key intermediates epoxide 12 and diol 17. The preparation of the properly functionalized epoxide 12 has been achieved in a straightforward fashion. However, all attempts to prepare tertiary alcohol 14 by reductive opening of 12 failed. In alternative exploratory efforts to achieve the same goal, allylic alcohols 16 and 29 were prepared by regioselective dehydration of diol 17. Whereas endo-isomer 16 was found to be reluctant to undergo catalytic hydrogenation, the exo counterpart 29 led to the undesired isomer affording after hydrolysis epi-C-8-dihydrovinigrol 32.

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“…Beyond the more familiar steric hindrance effects, use of functional groups as reagent hinges or leashes is now common. Our own studies of the latter phenomenon have focused on the heterogeneous catalytic hydrogenation of alkenes, − where profound changes in product stereochemistry may be generated by simple changes in such “spectator” functional groups. − These stereochemical results bear little relationship to the usual measures of group size, basicity or polarity alone but apparently represent complex combinations of such properties, tempered by the shape and accessibility of the influencing group . We term the net ability of such a group to enforce addition of hydrogen from its own face of the molecule “haptophilicity,” and have established a haptophilic order for a dozen of the most common functional groups. , Knowledge of group haptophilicities offers promise of stereochemical control in such reductions, but for a haptophilic order to be generally useful, it must be shown to apply to a variety of substrate systems.…”

Section: Introductionmentioning

confidence: 99%

Stereochemical Control of Reductions. 9. Haptophilicity Studies with 1,1-Disubstituted 2-Methyleneacenaphthenes

Thompson

Rashid

2002

J. Org. Chem.

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A series of 1-methyl-2-methyleneacenaphthenes has been synthesized, bearing an additional variable substituent (R) at the 1-position. These compounds have been hydrogenated in ethanol over a 5% Pd/C catalyst under standardized conditions in order to assess the haptophilicity of R, its ability to enforce addition of hydrogen from its own face of the molecule by coordination to the catalyst surface. The order of decreasing haptophilicity, assessed as the product epimer ratio, for the groups studied was R = CH(2)NH(2), CH(2)NMe(2), CH(2)OH, CHNOH, CH(2)OMe, CHO, CONH(2), CH(2)NHCOMe, COOK, COMe, CN, CONHOH, COOH, COOMe, COONa, COOLi. Because knowledge of group haptophilicities offers potential for stereochemical control in such reductions, comparisons are provided with haptophilic orders found in other molecular systems. It is shown that absolute haptophilicities can be manipulated by varying the dielectric constant of the solvent employed.

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Construction of cis- and trans-Decahydroisoquinolines via Heterogeneous Catalytic Hydrogenation

Cited by 14 publications

References 22 publications

Functional-Group-Directed Diastereoselective Hydrogenation of Aromatic Compounds. 1

Functional-Group-Directed Diastereoselective Hydrogenation of Aromatic Compounds. 1

Toward the Total Synthesis of Vinigrol: Synthesis of epi-C-8-Dihydrovinigrol

Stereochemical Control of Reductions. 9. Haptophilicity Studies with 1,1-Disubstituted 2-Methyleneacenaphthenes

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