Synthetic and Mechanistic Aspects of Palladium-Catalyzed Asymmetric Hydrocyanation of Alkenes. Crystal Structure and Reactions of (η2-Ethene)(diop)palladium

Martin Hodgson; David Parker; Richard J. Taylor; George Ferguson

doi:10.1021/om00098a011

Synthetic and Mechanistic Aspects of Palladium-Catalyzed Asymmetric Hydrocyanation of Alkenes. Crystal Structure and Reactions of (η2-Ethene)(diop)palladium

Martin Hodgson
, David Parker^*
, Richard J. Taylor
, George Ferguson

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Journal article › peer-review

65 Citations (Scopus)

Abstract

The asymmetric hydrocyanation of norbornene, catalyzed by chiral palladium diphosphine complexes, gives the exo nitrile with up to 40% enantiomeric excess. The mechanism has been studied by using (diop)PdC₂H₄ (6b) as a convenient precursor complex, whose crystal structure is reported. The crystals are monoclinic, space group P2₁with two molecules in a unit cell of dimensions a = 10.664 (3) Å, b = 11.023 (4) Å, c = 13.926 (2) Å, β = 109.41 (2)°; R = 0.034 for 2220 observed reflections. Principal dimensions include Pd—C(olefin) = 2.119 (8) and 2.122 (9) Å, Pd—P = 2.289 (2) Å, and C=C = 1.366 (11) Å. Intermediates in the catalytic cycle have been detected by NMR, including a hydrido cyanide and an alkyl cyanide.

Original language	English
Pages (from-to)	1761-1766
Number of pages	6
Journal	Organometallics
Volume	7
Issue number	8
DOIs	https://doi.org/10.1021/om00098a011
Publication status	Published - 1 Aug 1988

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@article{794a12dae0c942d39c33fd82b2831311,

title = "Synthetic and Mechanistic Aspects of Palladium-Catalyzed Asymmetric Hydrocyanation of Alkenes. Crystal Structure and Reactions of (η2-Ethene)(diop)palladium",

abstract = "The asymmetric hydrocyanation of norbornene, catalyzed by chiral palladium diphosphine complexes, gives the exo nitrile with up to 40\% enantiomeric excess. The mechanism has been studied by using (diop)PdC2H4 (6b) as a convenient precursor complex, whose crystal structure is reported. The crystals are monoclinic, space group P21with two molecules in a unit cell of dimensions a = 10.664 (3) {\AA}, b = 11.023 (4) {\AA}, c = 13.926 (2) {\AA}, β = 109.41 (2)°; R = 0.034 for 2220 observed reflections. Principal dimensions include Pd—C(olefin) = 2.119 (8) and 2.122 (9) {\AA}, Pd—P = 2.289 (2) {\AA}, and C=C = 1.366 (11) {\AA}. Intermediates in the catalytic cycle have been detected by NMR, including a hydrido cyanide and an alkyl cyanide.",

author = "Martin Hodgson and David Parker and Taylor, \{Richard J.\} and George Ferguson",

note = "Acknowledgment. We thank SERC, Glaxo Group pic (R.J.T.), and W.R. Grace Ltd. (M.H.) for support under the CASE scheme, and NSERC Canada for continuing support via operating grants. Publisher Copyright: {\textcopyright} 1988 American Chemical Society",

year = "1988",

month = aug,

day = "1",

doi = "10.1021/om00098a011",

language = "English",

volume = "7",

pages = "1761--1766",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "8",

}

TY - JOUR

T1 - Synthetic and Mechanistic Aspects of Palladium-Catalyzed Asymmetric Hydrocyanation of Alkenes. Crystal Structure and Reactions of (η2-Ethene)(diop)palladium

AU - Hodgson, Martin

AU - Parker, David

AU - Taylor, Richard J.

AU - Ferguson, George

N1 - Acknowledgment. We thank SERC, Glaxo Group pic (R.J.T.), and W.R. Grace Ltd. (M.H.) for support under the CASE scheme, and NSERC Canada for continuing support via operating grants. Publisher Copyright: © 1988 American Chemical Society

PY - 1988/8/1

Y1 - 1988/8/1

N2 - The asymmetric hydrocyanation of norbornene, catalyzed by chiral palladium diphosphine complexes, gives the exo nitrile with up to 40% enantiomeric excess. The mechanism has been studied by using (diop)PdC2H4 (6b) as a convenient precursor complex, whose crystal structure is reported. The crystals are monoclinic, space group P21with two molecules in a unit cell of dimensions a = 10.664 (3) Å, b = 11.023 (4) Å, c = 13.926 (2) Å, β = 109.41 (2)°; R = 0.034 for 2220 observed reflections. Principal dimensions include Pd—C(olefin) = 2.119 (8) and 2.122 (9) Å, Pd—P = 2.289 (2) Å, and C=C = 1.366 (11) Å. Intermediates in the catalytic cycle have been detected by NMR, including a hydrido cyanide and an alkyl cyanide.

AB - The asymmetric hydrocyanation of norbornene, catalyzed by chiral palladium diphosphine complexes, gives the exo nitrile with up to 40% enantiomeric excess. The mechanism has been studied by using (diop)PdC2H4 (6b) as a convenient precursor complex, whose crystal structure is reported. The crystals are monoclinic, space group P21with two molecules in a unit cell of dimensions a = 10.664 (3) Å, b = 11.023 (4) Å, c = 13.926 (2) Å, β = 109.41 (2)°; R = 0.034 for 2220 observed reflections. Principal dimensions include Pd—C(olefin) = 2.119 (8) and 2.122 (9) Å, Pd—P = 2.289 (2) Å, and C=C = 1.366 (11) Å. Intermediates in the catalytic cycle have been detected by NMR, including a hydrido cyanide and an alkyl cyanide.

UR - https://www.scopus.com/pages/publications/0001429223

U2 - 10.1021/om00098a011

DO - 10.1021/om00098a011

M3 - Journal article

AN - SCOPUS:0001429223

SN - 0276-7333

VL - 7

SP - 1761

EP - 1766

JO - Organometallics

JF - Organometallics

IS - 8

ER -

Synthetic and Mechanistic Aspects of Palladium-Catalyzed Asymmetric Hydrocyanation of Alkenes. Crystal Structure and Reactions of (η2-Ethene)(diop)palladium

Abstract

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