Intramolecular hydroamination/cyclization of aminoallenes catalyzed by organolanthanide complexes. Scope and mechanistic aspects

Victor M. Arredondo, Frank E. McDonald, Tobin J Marks

Research output: Contribution to journalArticle

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Abstract

Organolanthanide complexes of the general type Cp'2LnCH(TMS)2 (Cp' = η5-Me5C5; Ln = La, Sm, Y, Lu; TMS = SiMe3) serve as effective precatalysts for the rapid, regioselective, and highly diastereoselective intramolecular hydroamination/cyclization (IHC) of aminoallenes having the general formula RCH=C=CH(CH2)nCHR'NH2 to yield the corresponding heterocycles RCH=CHCHNHCH(R')(CH2)n-1CH2 (R = CH3, n-C3H7, n-C5H11; R' = H, CH3, n-C4H9, CH2=CHCH2CH2; n = 2, 3). The mono- and disubstituted pyrrolidines and piperidines produced bear an α-alkenyl functionality available for further synthetic manipulation. Kinetic and mechanistic data parallel organolanthanide-mediated intramolecular aminoalkene and aminoalkyne hydroamination/cyclization, implying turnover-limiting allene insertion into the Ln-N bond followed by rapid protonolysis of the resulting Ln-C bond. The reaction rate is zero-order in [aminoallene] and first-order in [catalyst] over 3 or more half-lives. Hydroamination/cyclization of monosubstituted aminoallenes (R = H; R' = H, CH3; n = 1, 2) is less regioselective, with tetrahydropyridines being the predominant products.

Original languageEnglish
Pages (from-to)1949-1960
Number of pages12
JournalOrganometallics
Volume18
Issue number10
Publication statusPublished - May 10 1999

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piperidine
Cyclization
bears
half life
manipulators
insertion
reaction kinetics
methylidyne
catalysts
kinetics
products
Pyrrolidines
Piperidines
Reaction rates
Catalysts
Kinetics

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Intramolecular hydroamination/cyclization of aminoallenes catalyzed by organolanthanide complexes. Scope and mechanistic aspects. / Arredondo, Victor M.; McDonald, Frank E.; Marks, Tobin J.

In: Organometallics, Vol. 18, No. 10, 10.05.1999, p. 1949-1960.

Research output: Contribution to journalArticle

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abstract = "Organolanthanide complexes of the general type Cp'2LnCH(TMS)2 (Cp' = η5-Me5C5; Ln = La, Sm, Y, Lu; TMS = SiMe3) serve as effective precatalysts for the rapid, regioselective, and highly diastereoselective intramolecular hydroamination/cyclization (IHC) of aminoallenes having the general formula RCH=C=CH(CH2)nCHR'NH2 to yield the corresponding heterocycles RCH=CHCHNHCH(R')(CH2)n-1CH2 (R = CH3, n-C3H7, n-C5H11; R' = H, CH3, n-C4H9, CH2=CHCH2CH2; n = 2, 3). The mono- and disubstituted pyrrolidines and piperidines produced bear an α-alkenyl functionality available for further synthetic manipulation. Kinetic and mechanistic data parallel organolanthanide-mediated intramolecular aminoalkene and aminoalkyne hydroamination/cyclization, implying turnover-limiting allene insertion into the Ln-N bond followed by rapid protonolysis of the resulting Ln-C bond. The reaction rate is zero-order in [aminoallene] and first-order in [catalyst] over 3 or more half-lives. Hydroamination/cyclization of monosubstituted aminoallenes (R = H; R' = H, CH3; n = 1, 2) is less regioselective, with tetrahydropyridines being the predominant products.",
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N2 - Organolanthanide complexes of the general type Cp'2LnCH(TMS)2 (Cp' = η5-Me5C5; Ln = La, Sm, Y, Lu; TMS = SiMe3) serve as effective precatalysts for the rapid, regioselective, and highly diastereoselective intramolecular hydroamination/cyclization (IHC) of aminoallenes having the general formula RCH=C=CH(CH2)nCHR'NH2 to yield the corresponding heterocycles RCH=CHCHNHCH(R')(CH2)n-1CH2 (R = CH3, n-C3H7, n-C5H11; R' = H, CH3, n-C4H9, CH2=CHCH2CH2; n = 2, 3). The mono- and disubstituted pyrrolidines and piperidines produced bear an α-alkenyl functionality available for further synthetic manipulation. Kinetic and mechanistic data parallel organolanthanide-mediated intramolecular aminoalkene and aminoalkyne hydroamination/cyclization, implying turnover-limiting allene insertion into the Ln-N bond followed by rapid protonolysis of the resulting Ln-C bond. The reaction rate is zero-order in [aminoallene] and first-order in [catalyst] over 3 or more half-lives. Hydroamination/cyclization of monosubstituted aminoallenes (R = H; R' = H, CH3; n = 1, 2) is less regioselective, with tetrahydropyridines being the predominant products.

AB - Organolanthanide complexes of the general type Cp'2LnCH(TMS)2 (Cp' = η5-Me5C5; Ln = La, Sm, Y, Lu; TMS = SiMe3) serve as effective precatalysts for the rapid, regioselective, and highly diastereoselective intramolecular hydroamination/cyclization (IHC) of aminoallenes having the general formula RCH=C=CH(CH2)nCHR'NH2 to yield the corresponding heterocycles RCH=CHCHNHCH(R')(CH2)n-1CH2 (R = CH3, n-C3H7, n-C5H11; R' = H, CH3, n-C4H9, CH2=CHCH2CH2; n = 2, 3). The mono- and disubstituted pyrrolidines and piperidines produced bear an α-alkenyl functionality available for further synthetic manipulation. Kinetic and mechanistic data parallel organolanthanide-mediated intramolecular aminoalkene and aminoalkyne hydroamination/cyclization, implying turnover-limiting allene insertion into the Ln-N bond followed by rapid protonolysis of the resulting Ln-C bond. The reaction rate is zero-order in [aminoallene] and first-order in [catalyst] over 3 or more half-lives. Hydroamination/cyclization of monosubstituted aminoallenes (R = H; R' = H, CH3; n = 1, 2) is less regioselective, with tetrahydropyridines being the predominant products.

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