Ligand effects in gold- and platinum-catalyzed cyclization of enynes: Chiral gold complexes for enantioselective alkoxycyclization

Maria Munoz-Herranz; Javier Adrio; Juan Carlos Carretero; Antonio M. Echavarren

doi:10.1021/om0491645

Ligand effects in gold- and platinum-catalyzed cyclization of enynes: Chiral gold complexes for enantioselective alkoxycyclization

Maria Munoz-Herranz
, Javier Adrio
, Juan Carlos Carretero
, Antonio M. Echavarren

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

280 Citations (Scopus)

Abstract

Phosphine and bidentate N-N ligands inhibit the Alder-ene-type cycloisomerization of enynes catalyzed by Pt(II) and favor the alkoxycyclization process. The enantioselective Pt(II)-catalyzed alkoxycyclization has been studied in the presence of chiral mono- and bidentate phosphines, as well as chiral bidentate N-N ligands. Modest levels of enantioselection (up to 50% ee) have been obtained with Tol-BINAP as ligand. The alkoxycyclizations with a catalyst formed from [Au(L)Cl]/AgX proceed more readily, and up to 94% ee's have been obtained using [(AuCl)₂(Tol-BINAP)] (47) as the precatalyst. The X-ray crystal structures of Au(I) complexes 47 and chloro-(R)-2-(tert-butylsulfenyl)-1-(diphenylphosphino)ferrocene gold(I) (39) show the AuCl fragments monocoordinated with the P centers of the chiral phosphine ligands.

Original language	English
Pages (from-to)	1293-1300
Number of pages	8
Journal	Organometallics
Volume	24
Issue number	6
DOIs	https://doi.org/10.1021/om0491645
Publication status	Published - 2005

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10.1021/om0491645

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@article{298e2dd383b64d96b0716d191ab6b39c,

title = "Ligand effects in gold- and platinum-catalyzed cyclization of enynes: Chiral gold complexes for enantioselective alkoxycyclization",

abstract = "Phosphine and bidentate N-N ligands inhibit the Alder-ene-type cycloisomerization of enynes catalyzed by Pt(II) and favor the alkoxycyclization process. The enantioselective Pt(II)-catalyzed alkoxycyclization has been studied in the presence of chiral mono- and bidentate phosphines, as well as chiral bidentate N-N ligands. Modest levels of enantioselection (up to 50\% ee) have been obtained with Tol-BINAP as ligand. The alkoxycyclizations with a catalyst formed from [Au(L)Cl]/AgX proceed more readily, and up to 94\% ee's have been obtained using [(AuCl)2(Tol-BINAP)] (47) as the precatalyst. The X-ray crystal structures of Au(I) complexes 47 and chloro-(R)-2-(tert-butylsulfenyl)-1-(diphenylphosphino)ferrocene gold(I) (39) show the AuCl fragments monocoordinated with the P centers of the chiral phosphine ligands.",

author = "Maria Munoz-Herranz and Javier Adrio and Carretero, \{Juan Carlos\} and Echavarren, \{Antonio M.\}",

year = "2005",

doi = "10.1021/om0491645",

language = "English",

volume = "24",

pages = "1293--1300",

journal = "Organometallics",

issn = "1520-6041",

publisher = "American Chemical Society",

number = "6",

}

TY - JOUR

T1 - Ligand effects in gold- and platinum-catalyzed cyclization of enynes: Chiral gold complexes for enantioselective alkoxycyclization

AU - Munoz-Herranz, Maria

AU - Adrio, Javier

AU - Carretero, Juan Carlos

AU - Echavarren, Antonio M.

PY - 2005

Y1 - 2005

N2 - Phosphine and bidentate N-N ligands inhibit the Alder-ene-type cycloisomerization of enynes catalyzed by Pt(II) and favor the alkoxycyclization process. The enantioselective Pt(II)-catalyzed alkoxycyclization has been studied in the presence of chiral mono- and bidentate phosphines, as well as chiral bidentate N-N ligands. Modest levels of enantioselection (up to 50% ee) have been obtained with Tol-BINAP as ligand. The alkoxycyclizations with a catalyst formed from [Au(L)Cl]/AgX proceed more readily, and up to 94% ee's have been obtained using [(AuCl)2(Tol-BINAP)] (47) as the precatalyst. The X-ray crystal structures of Au(I) complexes 47 and chloro-(R)-2-(tert-butylsulfenyl)-1-(diphenylphosphino)ferrocene gold(I) (39) show the AuCl fragments monocoordinated with the P centers of the chiral phosphine ligands.

AB - Phosphine and bidentate N-N ligands inhibit the Alder-ene-type cycloisomerization of enynes catalyzed by Pt(II) and favor the alkoxycyclization process. The enantioselective Pt(II)-catalyzed alkoxycyclization has been studied in the presence of chiral mono- and bidentate phosphines, as well as chiral bidentate N-N ligands. Modest levels of enantioselection (up to 50% ee) have been obtained with Tol-BINAP as ligand. The alkoxycyclizations with a catalyst formed from [Au(L)Cl]/AgX proceed more readily, and up to 94% ee's have been obtained using [(AuCl)2(Tol-BINAP)] (47) as the precatalyst. The X-ray crystal structures of Au(I) complexes 47 and chloro-(R)-2-(tert-butylsulfenyl)-1-(diphenylphosphino)ferrocene gold(I) (39) show the AuCl fragments monocoordinated with the P centers of the chiral phosphine ligands.

U2 - 10.1021/om0491645

DO - 10.1021/om0491645

M3 - Article

SN - 1520-6041

VL - 24

SP - 1293

EP - 1300

JO - Organometallics

JF - Organometallics

IS - 6

ER -