Effective, selective hydroalkoxylation/cyclization of alkynyl and allenyl alcohols mediated by lanthanide catalysts

Xianghua Yu; Sung Yong Seo; Tobin J. Marks

doi:10.1021/ja071707p

Effective, selective hydroalkoxylation/cyclization of alkynyl and allenyl alcohols mediated by lanthanide catalysts

Xianghua Yu, Sung Yong Seo, Tobin J. Marks^*

^*Corresponding author for this work

Chemistry

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

143 Scopus citations

Abstract

Catalytic hydroalkoxylation/cyclization reactions of alkynyl and allenyl alcohols are efficiently mediated by homoleptic lanthanide amides Ln[N(SiMe₃)₂]₃ (Ln = La, Nd, Sm, Y, and Lu). Conversions are found to be highly selective with products distinctly different from those produced by conventional transition metal catalysts. Turnover frequencies as high as 18.0 h^-1 at 60 °C are observed. Kinetic studies indicate that these transformations are zero-order in [substrate] and first-order in [catalyst]. Catalytic cycles are proposed in which insertion of C-C unsaturation into a Ln-O bond is turnover-limiting.

Original language	English (US)
Pages (from-to)	7244-7245
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	129
Issue number	23
DOIs	https://doi.org/10.1021/ja071707p
State	Published - Jun 13 2007

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Effective, selective hydroalkoxylation/cyclization of alkynyl and allenyl alcohols mediated by lanthanide catalysts",

abstract = "Catalytic hydroalkoxylation/cyclization reactions of alkynyl and allenyl alcohols are efficiently mediated by homoleptic lanthanide amides Ln[N(SiMe3)2]3 (Ln = La, Nd, Sm, Y, and Lu). Conversions are found to be highly selective with products distinctly different from those produced by conventional transition metal catalysts. Turnover frequencies as high as 18.0 h-1 at 60 °C are observed. Kinetic studies indicate that these transformations are zero-order in [substrate] and first-order in [catalyst]. Catalytic cycles are proposed in which insertion of C-C unsaturation into a Ln-O bond is turnover-limiting.",

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T1 - Effective, selective hydroalkoxylation/cyclization of alkynyl and allenyl alcohols mediated by lanthanide catalysts

AU - Yu, Xianghua

AU - Seo, Sung Yong

AU - Marks, Tobin J.

PY - 2007/6/13

Y1 - 2007/6/13

N2 - Catalytic hydroalkoxylation/cyclization reactions of alkynyl and allenyl alcohols are efficiently mediated by homoleptic lanthanide amides Ln[N(SiMe3)2]3 (Ln = La, Nd, Sm, Y, and Lu). Conversions are found to be highly selective with products distinctly different from those produced by conventional transition metal catalysts. Turnover frequencies as high as 18.0 h-1 at 60 °C are observed. Kinetic studies indicate that these transformations are zero-order in [substrate] and first-order in [catalyst]. Catalytic cycles are proposed in which insertion of C-C unsaturation into a Ln-O bond is turnover-limiting.

AB - Catalytic hydroalkoxylation/cyclization reactions of alkynyl and allenyl alcohols are efficiently mediated by homoleptic lanthanide amides Ln[N(SiMe3)2]3 (Ln = La, Nd, Sm, Y, and Lu). Conversions are found to be highly selective with products distinctly different from those produced by conventional transition metal catalysts. Turnover frequencies as high as 18.0 h-1 at 60 °C are observed. Kinetic studies indicate that these transformations are zero-order in [substrate] and first-order in [catalyst]. Catalytic cycles are proposed in which insertion of C-C unsaturation into a Ln-O bond is turnover-limiting.

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Effective, selective hydroalkoxylation/cyclization of alkynyl and allenyl alcohols mediated by lanthanide catalysts

Abstract

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