Cyclization of N-substituted diallylamines to pyrrolidine derivatives during the radical addition of perfluoroalkyl iodides

Brace, Neal O.

doi:10.1021/jo00820a024

Cited by 25 publications

(7 citation statements)

References 6 publications

(13 reference statements)

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“…Complexes 2 , 4 , 5 , 7 and 8 were obtained commercially. The following compounds have been previously described: 3 ,5 6 ,14 9 ,20 10 ,21 11 ,21 12 ,21 13 ,21 14 ,22 15 ,20 16 ,23 17 ,2b 19 ,24 20 ,25 21 ,26 22 ,20 23 ,27 24 ,22 25 ,22 27 ,22 28 ,20 29 ,28 32 ,20 33 ,29 36 ,30 37 ,31 39 ,28 40 ,20 41 ,20 42 ,32 44 ,33 45 ,28 46 ,34 47 ,2b 48 ,34 49 ,20 50 ,2b 51 ,2b 52 ,35 53 ,19 54 ,36 55 ,24 59 ,24 61 24…”

Section: Methodsmentioning

confidence: 99%

“…Complexes 2, 4, 5, 7 and 8 were obtained commercially. The following compounds have been previously described: 3, [5] 6, [14] 9, [20] 10, [21] 11, [21] 12, [21] 13, [21] 14, [22] 15, [20] 16, [23] 17, [2b] 19, [24] 20, [25] 21, [26] 22, [20] 23, [27] 24, [22] 25, [22] 27, [22] 28, [20] 29, [28] 32, [20] 33, [29] 36, [30] 37, [31] 39, [28] 40, [20] 41, [20] 42, [32] 44, [33] 45, [28] 46, [34] 47, [2b] 48, [34] 49, [20] 50, [2b] 51, [2b] 52, [35] 53, [19] 54, [36] 55, [24] 59, [24] 61. [24] General procedure for substrates synthesis: To a suspension of sodium hydride, in dry DMF, the starting material in solution, also in dry THF, was added dropwise at 0 8C.…”

Section: Methodsmentioning

confidence: 99%

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N‐Heterocyclic Carbene and Phosphine Ruthenium Indenylidene Precatalysts: A Comparative Study in Olefin Metathesis

Clavier

Nolan

2007

Chemistry A European J

139

104

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Kinetic studies on ring-closing metathesis of unhindered and hindered substrates using phosphine and N-heterocyclic carbene (NHC)-containing ruthenium-indenylidene complexes (first and second generation precatalysts, respectively) have been carried out. These studies reveal an appealing difference, between the phosphine and NHC-containing catalysts, associated with a distinctive rate-determining step in the reaction mechanism. These catalysts have been compared with the benzylidene generation catalysts and their respective representative substrates. Finally, the reaction scope of the two most interesting precatalysts, complexes that contain tricyclohexylphosphine and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (SIMes), has been investigated for the ring-closing and enyne metathesis for a large range of olefins. Owing to their high thermal stability, the SIMes-based indenylidene complexes were more efficient than their benzylidene analogues in the ring-closing metathesis of tetrasubstituted dienes. Importantly, none of the indenylidene precatalysts were found to be the most efficient for all of the substrates, indeed, a complementary complex-to-substrate activity relationship was observed.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

N‐Heterocyclic Carbene and Phosphine Ruthenium Indenylidene Precatalysts: A Comparative Study in Olefin Metathesis

Clavier

Nolan

2007

Chemistry A European J

139

104

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“…The major fraction contained 490 mg of a mixture of two products. Fractional recrystallization of the mixture gave 300 mg of N-(phenylsulfonyl)-2-methylenepiperidine (28), mp 94-95 °C, whose structure was assigned on the basis of its spectroscopic properties: IR (CHClg) 2950, 2840, 1660, 1605, 1440, 1350, 1165, 1010, 980, 920, and 620 cm'1; NMR (CDClg, 360 MHz) 1.66-1.72 (m, 2 H), 2.11 (t, 2 H ,J = 6.12 Hz), 3.10 (t, 2 H, J = 5.40 Hz), 3.54 The other component (150 mg) was assigned as IV-(phenylsulfonyl)-3-methyl-4-methylenepyrrolidine (27) on the basis of its 360-MHz NMR spectrum:…”

Section: Methodsmentioning

confidence: 99%

Synthesis of the pyrrolidine ring system by radical cyclization

Padwa¹,

Nimmesgern²,

Wong³

1985

J. Org. Chem.

121

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A series of bromo-substituted allyl-and diallyl-substituted sulfonamides have been found to undergo free radical cyclization when treated with tri-rc-butyltin hydride in the presence of AIBN. The regiochemical course of the cyclization depends on the nature of the substituent groups attached to the ir-bond. The stereoelectronic factors governing the cyclization reaction of these JV-allylsulfonamides are even more stringent than those which occur with the simple 5-hexenyl system. This is probably related to the shorter C-N bond distance which promotes the 5-exo trig cyclization pathway. The present method provides an attractive entry to the preparation of pyrrolidines from easily available N-(2-bromoethyl)-A-allyl-and N-(2-bromopropenyl) -IV-allylsulfonamides. The method represents a clear-cut example of the use of hetero-substituted radicals in C-C bond-forming processes.

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“…The following starting materials are prepared using literature methods: 32a ,24 32b ,24 32c ,25 32d ,26 32e ,26 32f ,27 32g 28. Carbene precursor salts IMes.HCl, IPr.HCl, IAda.HCl, I t Bu.HCl are commercially available from Strem Chemicals.…”

Section: Methodsmentioning

confidence: 99%

Triarylphosphine Ligands with Hemilabile Alkoxy Groups: Ligands for Nickel(II)‐Catalyzed Olefin Dimerization Reactions. Hydrovinylation of Vinylarenes, 1,3‐Dienes, and Cycloisomerization of 1,6‐Dienes

Biswas

Zhang²,

Raya³

et al. 2014

Adv Synth Catal

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Substitution of one of the phenyl groups of triphenylphosphine with a 2-benzyloxy-, 2-benzyloxymethyl- or 2-benzyloxyethyl-phenyl moiety results in a set of simple ligands, which exhibit strikingly different behaviour in various nickel(II)-catalyzed olefin dimerization reactions. Complexes of ligands with 2-benzyloxyphenyl-, 2-benzyloxymethylphenyl-diphenylphosphine (L5 and L6 respectively) are most active for hydrovinylation (HV) of vinylarenes, with the former leading to extensive isomerization of the primary 3-aryl-1-butenes into the conjugated 2-aryl-2-butenes even at −55 °C. However, 2-benzyloxymethyl-substituted ligand L6 is slightly less active, leading up to quantitative yields of the primary products of HV at ambient temperature with no trace of isomerization, thus providing the best option for a practical synthesis of these compounds. In sharp contrast, hydrovinylation of a variety of 1,3-dienes is best catalyzed by nickel(II)-complexes of 2-benzyloxyphenyldiphenylphosphine, L5. The other two ligands, 2-benzyloxymethyl-(L6) and 2-benzyloxyethyl-diphenylphosphine (L7) are much less effective in the HV of 1,3-dienes. Nickel(II)-catalyzed cycloisomerization of 1,6-dienes into methylenecyclopentanes, a reaction mechanistically related to the other hydrovinylation reactions, is also uniquely effected by nickel(II)-complexes of L5, but not of L6 or L7. In an attempt to prepare authentic samples of the methylencyclohexane products, nickel(II)-complexes of N-heterocyclic carbene-ligands were examined. In sharp contrast to the phosphines, which give the methylenecyclopentanes, methylenecyclohexanes are the major products in the (N-heterocyclic carbene)nickel(II)-mediated reactions.

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Cyclization of N-substituted diallylamines to pyrrolidine derivatives during the radical addition of perfluoroalkyl iodides

Cited by 25 publications

References 6 publications

N‐Heterocyclic Carbene and Phosphine Ruthenium Indenylidene Precatalysts: A Comparative Study in Olefin Metathesis

N‐Heterocyclic Carbene and Phosphine Ruthenium Indenylidene Precatalysts: A Comparative Study in Olefin Metathesis

Synthesis of the pyrrolidine ring system by radical cyclization

Triarylphosphine Ligands with Hemilabile Alkoxy Groups: Ligands for Nickel(II)‐Catalyzed Olefin Dimerization Reactions. Hydrovinylation of Vinylarenes, 1,3‐Dienes, and Cycloisomerization of 1,6‐Dienes

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