Hydroformylation of 1,4-diolefins in the presence of primary amines leading to heterocyclic compounds

Kranemann, Christian L.; Kitsos‐Rzychon, Beate E.; Eilbracht, Peter

doi:10.1016/s0040-4020(99)00162-3

Cited by 34 publications

(24 citation statements)

References 20 publications

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“…Their formation can be rationalized in terms of a mechanism akin to that delineated for the synthesis of pyrroles starting from 1,4-pentadienes under hydroformylation conditions. [14] The 1,5-diazacyclooctanes 6a and 6b both result from an iso,iso-hydroformylation process. A nine-membered ring product, as might be expected [13] to result from an n,isohydroformylation, is not observed.…”

Section: Resultsmentioning

confidence: 99%

“…1,25.8,28.8,29.4 (CH,8),31.5,31.8,32.5 (CH 2 ,7), 50. 4, 50.8, 51.0, 51.3, 51.3, 51.5, 51.5 (2 ϫ CH 2 , 4 ϩ 6), 46.3, 49.0, 51.7, 54.1 (CH 2 ,9),58.5,58.6,59.0,59.2 (CH 2 ,15),126.6,126.7,126.7 (CH,19), 127.9, 128.0, 128.0 (CH,17/18),128.8,128.9,129.1 (CH,18/17),139.6,139.7,139.9,140 (11), 65 (16), 41 (14). Ϫ C 29 H 43 N 3 O (449.7): calcd.…”

Section: Reaction Of N-acetyldiallylamine (1a) With 2-propylamine (4bmentioning

confidence: 99%

“…C 77. 7, H 9.8, N 9.1; found C 77.5, H 9.5, N 8.7. Reaction of N-Acetyldimethallylamine (1c) with 2,6-Bis(benzylaminomethyl)pyridine (5f): 1c (132 mg, 0.8 mmol), 5f (250 mg, 0.8 mmol), [Rh(cod)Cl] 2 (3 mg, 0.5 mol-%), and dioxane (100 mL) were placed in an autoclave, and the mixture was pressurized and heated to 120°C for 70 h. The crude reaction products (500 mg) were purified by column chromatography with MTBE/petroleum ether (PE), 1:1, as eluent to give 226 mg (0.4 mmol, 56%) of 8-acetyl-3,13-dibenzyl-6,10-dimethyl-3,8,13,19-tetraazabicyclo-[13.3.1]nonadeca-1 (18),15 (19),16-triene (14). (9 H,benzyl CH 2 ),7.11 (d,2 H,3 J ϭ 7.5 Hz,7.25 (m,10 H,benzyl),7.60 (m,1 H,.…”

Section: Reaction Of N-acetyldimethallylamine (1c) With 14-bis(ethylmentioning

confidence: 99%

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A New and Versatile Access to Polyazamacroheterocycles and Cryptands Through Ring-Closing Bis(hydroaminomethylation)

Kranemann

Eilbracht

2000

Eur. J. Org. Chem.

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The RhI‐catalyzed hydroformylation of dienes in the presence of primary amines or secondary α,ω‐diamines has been applied to macroheterocyclic ring synthesis. Starting from (hetero)diallylic systems, 12‐ to 36‐membered polyheterocycles have been readily obtained in up to 56% yield. In addition, we show that the macrocyclic systems thus obtained can be debenzylated and that the resulting macrocyclic diamines undergo a second ring‐closing bis(hydroaminomethylation) to give cryptand systems.

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Section: Resultsmentioning

confidence: 99%

Section: Reaction Of N-acetyldiallylamine (1a) With 2-propylamine (4bmentioning

confidence: 99%

Section: Reaction Of N-acetyldimethallylamine (1c) With 14-bis(ethylmentioning

confidence: 99%

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A New and Versatile Access to Polyazamacroheterocycles and Cryptands Through Ring-Closing Bis(hydroaminomethylation)

Kranemann

Eilbracht

2000

Eur. J. Org. Chem.

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“…[6] Tr ansition metal-catalyzed cyclization/ring expansion of functionalized alkynes, [7] hydroformylation of 1,4-dienes followed by condensation with primary amines, [8] and other reactions [9] have also been applied for the synthesis of cyclopenta[b]pyrrole derivatives.…”

mentioning

confidence: 99%

“…To our delight, a1 :1 molar ratio reactiono ccurred in the presence of 50 mol% p-TsOH·H 2 Oa st he promoter in dichloromethane at ambient temperature,f orming the target product 3a in 32% yield with excellent diastereoselectivity (dr > 20:1) ( Among the tested solvents (dichloromethane,1 ,2-dichloroethane,a cetonitrile, toluene andT HF), bothd ichloromethane and1 ,2-dichloroethane were found to provide suitabler eactionm edia, in contrast, the reaction hardly proceeded in THF (Table 1, entries 5a nd [8][9][10][11]. Elevating the reactiont emperature to 40-60 8 8C loweredt he formation of 3a (Table 1, entries 12 and 13).…”

mentioning

confidence: 99%

Brønsted Acid‐Promoted Cascade Alkylation/Cyclization of Pyrroles with N,N‐Dimethylaminomethyleneglutaconic Acid Dinitrile: A Concise Route to Cyclopenta[b]pyrroles

Chen

et al. 2015

Adv Synth Catal

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AB r ønsted acid (p-TsOH·H 2 O) promoted alkylation/cyclization cascade reactiono fp yrroles with N,N-dimethylaminomethyleneglutaconic acid dinitrile was efficiently realized to afford functionalized cyclopenta [b]pyrroles with excellent diastereoselectivity.D eamination of the corresponding ammonium saltso ft he cyclopenta [b]pyrroles with methyl iodide led to dihydrocyclopenta[c]pyrroles. Thec ascade reactionp athway was confirmed by isolation and transformation of the reactioni ntermediate,i .e., the 2-alkylated pyrrole.Keywords: Brønsted acid;c yclization; cyclopenta [b]pyrroles; N,N-dimethylaminomethyleneglutaconic acid dinitrile;pyrroles Fused heterocyclic compoundsc ontainingacyclopenta [b]pyrrole motif are present in many biologically active natural products andm edicinallyi mportant compounds, [1] such as,k rill fluorescent substance F [2] which is ac omponent of the phorbine chromophore presenti na ll types of chlorophylls,r oseophilin, [1c,3] and an inhibitor of d-amino oxidase [4] (Figure 1). Consequently,m uch effort has recentlyb een devoted to the synthesis of cyclopenta [b]pyrrole derivatives.T he acid-mediated Nazarov cyclization is au seful method for the constructiono ff ive-membered carbocycles, [5] which has usuallyb een employed as as traightforward route to access cyclopentenone-fused pyrroles.[6] Tr ansition metal-catalyzed cyclization/ring expansion of functionalized alkynes, [7] hydroformylation of 1,4-dienes followed by condensation with primary amines, [8] and other reactions [9] have also been applied for the synthesis of cyclopenta[b]pyrrole derivatives.Brønsted or Lewis acid-promoted Friedel-Crafts cyclization has been considereda sapowerful method to prepare heterocyclic compounds.[10] Ap yrrole ring can thusb eu sed as the "template"-like structure to establish another ring onto it for the construction of polycyclic compounds, [11] in which annulation of prefunctionalized alkynes or olefins to ap yrrole core is usuallyi nvolved. After screening of the relevant known synthetic methods, we reasonedt hat ad iene might be utilized to replace the pre-functionalized alkyneso ro lefins for the same purpose.T he polarized diene, N,N-dimethylaminomethyleneglutaconic acid dinitrile, [12] which is structurally endowedw ith an electron-donating NMe 2 moiety andt wo electronwithdrawing cyano groups attacheda ti ts two C=C bonds,h as been useda saC 3 building block to synthesize carbocyclic compounds.[13] Recently,w ef ound that Brønsted acids could promote Friedel-Crafts alkylationo fi ndoles with N,N-dimethylaminomethy-

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Carbonylation

2012

Organic Synthesis Using Transition Metals

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Carbon monoxide, with the use of transition-metal catalysis, has become a valuable C1 building block. 1 Carbonylation is one method of intercepting the palladium intermediates generated by oxidative addition. 2 If the reaction is run under at atmosphere of carbon monoxide, then the palladium intermediate may undergo CO insertion, generating an 1 -acyl complex, before any other reagent (Scheme 4.1). Whether it will do so in useful quantities is a question of kinetics: will the rate of CO insertion be faster than the rates of the other possible processes? The reactivity of the other reagents may be reduced by careful choice of functionality, or their concentration may be reduced by slow addition, perhaps by use of a syringe pump. The rate of reactions involving carbon monoxide may be increased by the use of higher pressures. While many reactions proceed satisfactorily at atmospheric pressure, other reactions require increased pressures. Pressures up to 100 psi may be safely attained in good quality, heavy-wall glass vessels, fitted with a pressure head and safety release valve, and operated behind a safety shield. Much higher pressures may be achieved using steel autoclaves. * Carbonylative Coupling Reactions: Synthesis of Carbonyl DerivativesCan we intercept the acyl intermediate with a main-group organometallic, or other carbon nucleophile? This could be a useful synthesis of ketones (Scheme 4.2). 3 How would the mechanism work? It would require coordination and insertion of CO before reductive elimination (Scheme 4.3). As reductive elimination is usually fast, CO must be involved before transmetallation. Ketone production will be favoured over direct coupling if the rate of CO insertion is faster than the rate of transmetallation of L 2 PdR'X. We can make CO chemistry faster by increasing the pressure; we can make transmetallation slower by using a less-reactive organometallic, and also by slow addition, to get the right kinetics. Although slow transmetallation is favoured by the use of less electropositive metals, M, such as tin, boron and silicon, a wide range of organometallics have been employed too. In addition to tin (Schemes 4.4 and 4.5) 4,5 , boron (Scheme 4.6) 6 and silicon (Scheme 4.7), 7 examples include aluminium (Scheme 4.8) 8 and zinc (Scheme 4.9) 9 . * WARNING Carbon monoxide is highly toxic. All reactions using this gas should be carried out in an efficient fume cupboard. Reactions under pressure should be carried out behind additional safety shielding.

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Hydroformylation of 1,4-diolefins in the presence of primary amines leading to heterocyclic compounds

Cited by 34 publications

References 20 publications

A New and Versatile Access to Polyazamacroheterocycles and Cryptands Through Ring-Closing Bis(hydroaminomethylation)

A New and Versatile Access to Polyazamacroheterocycles and Cryptands Through Ring-Closing Bis(hydroaminomethylation)

Brønsted Acid‐Promoted Cascade Alkylation/Cyclization of Pyrroles with N,N‐Dimethylaminomethyleneglutaconic Acid Dinitrile: A Concise Route to Cyclopenta[b]pyrroles

Carbonylation

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