Heavier group-2-element catalyzed hydroamination of carbodiimides

Jennifer R. Lachs; Anthony G.M. Barrett; Mark R. Crimmin; Gabriele Kociok-Köhn; Michael S. Hill; Mary F. Mahon; Panayiotis A. Procopiou

doi:10.1002/ejic.200800613

Heavier group-2-element catalyzed hydroamination of carbodiimides

Jennifer R. Lachs
, Anthony G.M. Barrett
, Mark R. Crimmin
, Gabriele Kociok-Köhn
, Michael S. Hill
, Mary F. Mahon
, Panayiotis A. Procopiou

Imperial College London
University of Bath
GlaxoSmithKline

Research output: Contribution to journal › Article › peer-review

80 Citations (SciVal)

Abstract

The heteroleptic calcium amide [{ArNC(Me)CHC(Me)-NAr}Ca{N(SiMe ₃)₂}(THF)] (Ar = 2,6-diisopropylphenyl) and the homoleptic heavier alkaline earth amides, [M{N(Si-Me₃)₂} ₂(THF)2] (M = Ca, Sr and Ba) are reported as competent pre-catalysts for the hydroamination of 1,3-carbodiimides. Whilst the reaction scope is currently limited to reactions of aromatic amines with 1,3-dialkylcarbodiimides, in most cases preparations in hydrocarbon solvents proceed rapidly at room temperature with catalyst loadings as low as 0.2 mol-% and the guanidine reaction products crystallize directly from the reaction mixture. Initial studies are consistent with the intermediacy of heavier group-2 guanidinate complexes.

Original language	English
Pages (from-to)	4173-4179
Number of pages	7
Journal	European Journal of Inorganic Chemistry
Issue number	26
DOIs	https://doi.org/10.1002/ejic.200800613
Publication status	Published - 1 Sept 2008

Keywords

Alkaline earth amides
Guanidinate
Guanidine
Hydroamination

ASJC Scopus subject areas

Inorganic Chemistry

Access to Document

10.1002/ejic.200800613

Cite this

@article{2f9f1a53e9ef4bbdbbb8d3461e25576d,

title = "Heavier group-2-element catalyzed hydroamination of carbodiimides",

abstract = "The heteroleptic calcium amide [\{ArNC(Me)CHC(Me)-NAr\}Ca\{N(SiMe 3)2\}(THF)] (Ar = 2,6-diisopropylphenyl) and the homoleptic heavier alkaline earth amides, [M\{N(Si-Me3)2\} 2(THF)2] (M = Ca, Sr and Ba) are reported as competent pre-catalysts for the hydroamination of 1,3-carbodiimides. Whilst the reaction scope is currently limited to reactions of aromatic amines with 1,3-dialkylcarbodiimides, in most cases preparations in hydrocarbon solvents proceed rapidly at room temperature with catalyst loadings as low as 0.2 mol-\% and the guanidine reaction products crystallize directly from the reaction mixture. Initial studies are consistent with the intermediacy of heavier group-2 guanidinate complexes.",

keywords = "Alkaline earth amides, Guanidinate, Guanidine, Hydroamination",

author = "Lachs, \{Jennifer R.\} and Barrett, \{Anthony G.M.\} and Crimmin, \{Mark R.\} and Gabriele Kociok-K{\"o}hn and Hill, \{Michael S.\} and Mahon, \{Mary F.\} and Procopiou, \{Panayiotis A.\}",

year = "2008",

month = sep,

day = "1",

doi = "10.1002/ejic.200800613",

language = "English",

pages = "4173--4179",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH Verlag",

number = "26",

}

TY - JOUR

T1 - Heavier group-2-element catalyzed hydroamination of carbodiimides

AU - Lachs, Jennifer R.

AU - Barrett, Anthony G.M.

AU - Crimmin, Mark R.

AU - Kociok-Köhn, Gabriele

AU - Hill, Michael S.

AU - Mahon, Mary F.

AU - Procopiou, Panayiotis A.

PY - 2008/9/1

Y1 - 2008/9/1

N2 - The heteroleptic calcium amide [{ArNC(Me)CHC(Me)-NAr}Ca{N(SiMe 3)2}(THF)] (Ar = 2,6-diisopropylphenyl) and the homoleptic heavier alkaline earth amides, [M{N(Si-Me3)2} 2(THF)2] (M = Ca, Sr and Ba) are reported as competent pre-catalysts for the hydroamination of 1,3-carbodiimides. Whilst the reaction scope is currently limited to reactions of aromatic amines with 1,3-dialkylcarbodiimides, in most cases preparations in hydrocarbon solvents proceed rapidly at room temperature with catalyst loadings as low as 0.2 mol-% and the guanidine reaction products crystallize directly from the reaction mixture. Initial studies are consistent with the intermediacy of heavier group-2 guanidinate complexes.

AB - The heteroleptic calcium amide [{ArNC(Me)CHC(Me)-NAr}Ca{N(SiMe 3)2}(THF)] (Ar = 2,6-diisopropylphenyl) and the homoleptic heavier alkaline earth amides, [M{N(Si-Me3)2} 2(THF)2] (M = Ca, Sr and Ba) are reported as competent pre-catalysts for the hydroamination of 1,3-carbodiimides. Whilst the reaction scope is currently limited to reactions of aromatic amines with 1,3-dialkylcarbodiimides, in most cases preparations in hydrocarbon solvents proceed rapidly at room temperature with catalyst loadings as low as 0.2 mol-% and the guanidine reaction products crystallize directly from the reaction mixture. Initial studies are consistent with the intermediacy of heavier group-2 guanidinate complexes.

KW - Alkaline earth amides

KW - Guanidinate

KW - Guanidine

KW - Hydroamination

UR - https://www.scopus.com/pages/publications/53549127283

U2 - 10.1002/ejic.200800613

DO - 10.1002/ejic.200800613

M3 - Article

AN - SCOPUS:53549127283

SN - 1434-1948

SP - 4173

EP - 4179

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 26

ER -

Heavier group-2-element catalyzed hydroamination of carbodiimides

Abstract

Keywords

ASJC Scopus subject areas

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Hydroamination of Alkenes and Alkynes with Group 2 Centred Catalysts

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Heavier group-2-element catalyzed hydroamination of carbodiimides

Abstract

Keywords

ASJC Scopus subject areas

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Fingerprint

Projects

Hydroamination of Alkenes and Alkynes with Group 2 Centred Catalysts

Cite this