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

Annika Friberg; Ian Sarvary; Ola Wendt; Torbjörn Frejd

doi:10.1016/j.tetasy.2008.07.006

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

Annika Friberg, Ian Sarvary, Ola Wendt, Torbjörn Frejd

Centre for Analysis and Synthesis

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

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.

Original language	English
Pages (from-to)	1765-1777
Journal	Tetrahedron: Asymmetry
Volume	19
Issue number	15
DOIs	https://doi.org/10.1016/j.tetasy.2008.07.006
Publication status	Published - 2008

Bibliographical note

The information about affiliations in this record was updated in December 2015.
The record was previously connected to the following departments: Organic chemistry (S/LTH) (011001240)

Subject classification (UKÄ)

Organic Chemistry

Access to Document

10.1016/j.tetasy.2008.07.006

Cite this

@article{cc3538e080d043e4b0047340f45b96aa,

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

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 = "Annika Friberg and Ian Sarvary and Ola Wendt and Torbj{\"o}rn Frejd",

note = "The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Organic chemistry (S/LTH) (011001240)",

year = "2008",

doi = "10.1016/j.tetasy.2008.07.006",

language = "English",

volume = "19",

pages = "1765--1777",

journal = "Tetrahedron: Asymmetry",

issn = "0957-4166",

publisher = "Elsevier",

number = "15",

}

TY - JOUR

T1 - Bicyclo[2.2.2]octane-derived chiral ligands-synthesis and application of BODOLs in the asymmetric reduction of acetophenone with catecholborane

AU - Friberg, Annika

AU - Sarvary, Ian

AU - Wendt, Ola

AU - Frejd, Torbjörn

N1 - The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Organic chemistry (S/LTH) (011001240)

PY - 2008

Y1 - 2008

N2 - 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.

AB - 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.

U2 - 10.1016/j.tetasy.2008.07.006

DO - 10.1016/j.tetasy.2008.07.006

M3 - Article

SN - 0957-4166

VL - 19

SP - 1765

EP - 1777

JO - Tetrahedron: Asymmetry

JF - Tetrahedron: Asymmetry

IS - 15

ER -

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

Abstract

Bibliographical note

Subject classification (UKÄ)

Access to Document

Fingerprint

Cite this