1996 Merck Frosst Award Lecture Synthetic adventures along a Rocky Mountain road
This paper describes the chemistry presented during the Merck Frosst Centre for Therapeutic Research Lecture Award given at the 79th Chemistry in Canada Conference held in St. John's, Newfoundland in June 1996. The first section describes the synthesis of (+)-xestoquinone using an asymmetric pa...
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crcansciencepubl:10.1139/v97-139 2023-12-17T10:44:56+01:00 1996 Merck Frosst Award Lecture Synthetic adventures along a Rocky Mountain road Keay, Brian A. Maddaford, Shawn P. Cristofoli, Walter A. Andersen, Neil G. Passafaro, Marco S. Wilson, Noel S. Nieman, James A. 1997 http://dx.doi.org/10.1139/v97-139 http://www.nrcresearchpress.com/doi/pdf/10.1139/v97-139 en eng Canadian Science Publishing http://www.nrcresearchpress.com/page/about/CorporateTextAndDataMining Canadian Journal of Chemistry volume 75, issue 9, page 1163-1171 ISSN 0008-4042 1480-3291 Organic Chemistry General Chemistry Catalysis journal-article 1997 crcansciencepubl https://doi.org/10.1139/v97-139 2023-11-19T13:38:29Z This paper describes the chemistry presented during the Merck Frosst Centre for Therapeutic Research Lecture Award given at the 79th Chemistry in Canada Conference held in St. John's, Newfoundland in June 1996. The first section describes the synthesis of (+)-xestoquinone using an asymmetric palladium-catalyzed polyene cyclization as the key step that creates the C and D rings and the stereogenic centre (68% ee) in one step. Extensions of the work involving an in situ Suzuki reaction are presented. The synthesis of C 2 -symmetric biaryls and the synthesis of a recently isolated binaphthyl natural product is described using this new method. A new one-pot desilylation–oxidation procedure of silyl ethers is described in detail for the preparation of aldehydes and ketones directly without the need for the isolation of the alcohol intermediate. Finally, a highly diastereoselective (>97%) Diels–Alder reaction is presented using (+)-cis,cis-spiro[4.4]nonane-1,6-diol as a new chiral auxiliary. One of the alcohols is attached to a pivalate, the other to an acrylate, and the Diels–Alder reaction with cyclopentadiene provides only one adduct (by 1 H NMR and HPLC) with the endo stereochemistry. Keywords: (+)-xestoquinone, asymmetric palladium-catalyzed polyene cyclization, in situ Suzuki reaction, desilylation–oxidation reaction, spirodiols, chiral auxiliaries. Article in Journal/Newspaper Newfoundland Canadian Science Publishing (via Crossref) Canada Spiro ENVELOPE(-59.000,-59.000,-62.267,-62.267) Canadian Journal of Chemistry 75 9 1163 1171 |
institution |
Open Polar |
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Canadian Science Publishing (via Crossref) |
op_collection_id |
crcansciencepubl |
language |
English |
topic |
Organic Chemistry General Chemistry Catalysis |
spellingShingle |
Organic Chemistry General Chemistry Catalysis Keay, Brian A. Maddaford, Shawn P. Cristofoli, Walter A. Andersen, Neil G. Passafaro, Marco S. Wilson, Noel S. Nieman, James A. 1996 Merck Frosst Award Lecture Synthetic adventures along a Rocky Mountain road |
topic_facet |
Organic Chemistry General Chemistry Catalysis |
description |
This paper describes the chemistry presented during the Merck Frosst Centre for Therapeutic Research Lecture Award given at the 79th Chemistry in Canada Conference held in St. John's, Newfoundland in June 1996. The first section describes the synthesis of (+)-xestoquinone using an asymmetric palladium-catalyzed polyene cyclization as the key step that creates the C and D rings and the stereogenic centre (68% ee) in one step. Extensions of the work involving an in situ Suzuki reaction are presented. The synthesis of C 2 -symmetric biaryls and the synthesis of a recently isolated binaphthyl natural product is described using this new method. A new one-pot desilylation–oxidation procedure of silyl ethers is described in detail for the preparation of aldehydes and ketones directly without the need for the isolation of the alcohol intermediate. Finally, a highly diastereoselective (>97%) Diels–Alder reaction is presented using (+)-cis,cis-spiro[4.4]nonane-1,6-diol as a new chiral auxiliary. One of the alcohols is attached to a pivalate, the other to an acrylate, and the Diels–Alder reaction with cyclopentadiene provides only one adduct (by 1 H NMR and HPLC) with the endo stereochemistry. Keywords: (+)-xestoquinone, asymmetric palladium-catalyzed polyene cyclization, in situ Suzuki reaction, desilylation–oxidation reaction, spirodiols, chiral auxiliaries. |
format |
Article in Journal/Newspaper |
author |
Keay, Brian A. Maddaford, Shawn P. Cristofoli, Walter A. Andersen, Neil G. Passafaro, Marco S. Wilson, Noel S. Nieman, James A. |
author_facet |
Keay, Brian A. Maddaford, Shawn P. Cristofoli, Walter A. Andersen, Neil G. Passafaro, Marco S. Wilson, Noel S. Nieman, James A. |
author_sort |
Keay, Brian A. |
title |
1996 Merck Frosst Award Lecture Synthetic adventures along a Rocky Mountain road |
title_short |
1996 Merck Frosst Award Lecture Synthetic adventures along a Rocky Mountain road |
title_full |
1996 Merck Frosst Award Lecture Synthetic adventures along a Rocky Mountain road |
title_fullStr |
1996 Merck Frosst Award Lecture Synthetic adventures along a Rocky Mountain road |
title_full_unstemmed |
1996 Merck Frosst Award Lecture Synthetic adventures along a Rocky Mountain road |
title_sort |
1996 merck frosst award lecture synthetic adventures along a rocky mountain road |
publisher |
Canadian Science Publishing |
publishDate |
1997 |
url |
http://dx.doi.org/10.1139/v97-139 http://www.nrcresearchpress.com/doi/pdf/10.1139/v97-139 |
long_lat |
ENVELOPE(-59.000,-59.000,-62.267,-62.267) |
geographic |
Canada Spiro |
geographic_facet |
Canada Spiro |
genre |
Newfoundland |
genre_facet |
Newfoundland |
op_source |
Canadian Journal of Chemistry volume 75, issue 9, page 1163-1171 ISSN 0008-4042 1480-3291 |
op_rights |
http://www.nrcresearchpress.com/page/about/CorporateTextAndDataMining |
op_doi |
https://doi.org/10.1139/v97-139 |
container_title |
Canadian Journal of Chemistry |
container_volume |
75 |
container_issue |
9 |
container_start_page |
1163 |
op_container_end_page |
1171 |
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1785564568735449088 |