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Bicyclo[2.2.2]octane-derived chiral ligands-synthesis and application of BODOLs in the asymmetric reduction of acetophenone with catecholborane

Friberg, Annika LU ; Sarvary, Ian; Wendt, Ola LU and Frejd, Torbjörn LU (2008) In Tetrahedron: Asymmetry 19(15). p.1765-1777
Abstract
An improved synthetic route to the bicyclo[2.2.2]octane-2,6-diol ligands (2,6-BODOLS) allowed an increased structural variation of the ligand side-arm. The addition of aromatic or vinylic Grignard reagents to hydroxyketone 1 was highly selective and ligands 3f-3I were isolated in 84-97% yield. The addition of alkyl Grignard reagents containing beta-hydrogens resulted in lower yields (13-71%) due to competing ketone reduction. A number of 2,5-BODOLs were synthesized using a similar methodology. The ligands, together with Ti(OiPr)(4), were tested in the asymmetric reduction of acetophenone with catecholborane (up to 98% ee). 1-Naphthyl-BODOL 3i was employed as an allylboration reagent to benzaldehyde together with Sc(OTf)(3), resulting in... (More)
An improved synthetic route to the bicyclo[2.2.2]octane-2,6-diol ligands (2,6-BODOLS) allowed an increased structural variation of the ligand side-arm. The addition of aromatic or vinylic Grignard reagents to hydroxyketone 1 was highly selective and ligands 3f-3I were isolated in 84-97% yield. The addition of alkyl Grignard reagents containing beta-hydrogens resulted in lower yields (13-71%) due to competing ketone reduction. A number of 2,5-BODOLs were synthesized using a similar methodology. The ligands, together with Ti(OiPr)(4), were tested in the asymmetric reduction of acetophenone with catecholborane (up to 98% ee). 1-Naphthyl-BODOL 3i was employed as an allylboration reagent to benzaldehyde together with Sc(OTf)(3), resulting in (1S)-1-phenyl-3-buten-1-ol in 80% ee. (C) 2008 Elsevier Ltd. All rights reserved. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Tetrahedron: Asymmetry
volume
19
issue
15
pages
1765 - 1777
publisher
Elsevier
external identifiers
  • wos:000259623600002
  • scopus:49049087875
ISSN
0957-4166
DOI
10.1016/j.tetasy.2008.07.006
language
English
LU publication?
yes
id
cc3538e0-80d0-43e4-b004-7340f45b96aa (old id 1286922)
date added to LUP
2009-01-29 15:16:11
date last changed
2017-01-01 05:25:25
@article{cc3538e0-80d0-43e4-b004-7340f45b96aa,
  abstract     = {An improved synthetic route to the bicyclo[2.2.2]octane-2,6-diol ligands (2,6-BODOLS) allowed an increased structural variation of the ligand side-arm. The addition of aromatic or vinylic Grignard reagents to hydroxyketone 1 was highly selective and ligands 3f-3I were isolated in 84-97% yield. The addition of alkyl Grignard reagents containing beta-hydrogens resulted in lower yields (13-71%) due to competing ketone reduction. A number of 2,5-BODOLs were synthesized using a similar methodology. The ligands, together with Ti(OiPr)(4), were tested in the asymmetric reduction of acetophenone with catecholborane (up to 98% ee). 1-Naphthyl-BODOL 3i was employed as an allylboration reagent to benzaldehyde together with Sc(OTf)(3), resulting in (1S)-1-phenyl-3-buten-1-ol in 80% ee. (C) 2008 Elsevier Ltd. All rights reserved.},
  author       = {Friberg, Annika and Sarvary, Ian and Wendt, Ola and Frejd, Torbjörn},
  issn         = {0957-4166},
  language     = {eng},
  number       = {15},
  pages        = {1765--1777},
  publisher    = {Elsevier},
  series       = {Tetrahedron: Asymmetry},
  title        = {Bicyclo[2.2.2]octane-derived chiral ligands-synthesis and application of BODOLs in the asymmetric reduction of acetophenone with catecholborane},
  url          = {http://dx.doi.org/10.1016/j.tetasy.2008.07.006},
  volume       = {19},
  year         = {2008},
}