Asymmetric Hydrosilylation of Ketones Using Trans-Chelating Chiral Peralkylbisphosphine Ligands Bearing Primary Alkyl Substituents on Phosphorus Atoms

Asymmetric hydrosilylation of simple ketones with diphenylsilane proceeded at -40 °C in the presence of a rhodium complex (0.001—0.01 molar amount) coordinated with a trans-chelating chiral bisphosphine ligand bearing linear alkyl substituents on the phosphorus atoms, (R,R)-(S,S)-Et-, Pr-, or BuTRAP...

Full description

Saved in:
Bibliographic Details
Published in:Bulletin of the Chemical Society of Japan 2000-02, Vol.73 (2), p.485-496
Main Authors: Kuwano, Ryoichi, Sawamura, Masaya, Shirai, Junya, Takahashi, Masatoshi, Ito, Yoshihiko
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
cited_by cdi_FETCH-LOGICAL-c443t-5c46088a41be47a001332b207e9e2a16b01125d7d30885dc9363abf1392d2ab23
cites cdi_FETCH-LOGICAL-c443t-5c46088a41be47a001332b207e9e2a16b01125d7d30885dc9363abf1392d2ab23
container_end_page 496
container_issue 2
container_start_page 485
container_title Bulletin of the Chemical Society of Japan
container_volume 73
creator Kuwano, Ryoichi
Sawamura, Masaya
Shirai, Junya
Takahashi, Masatoshi
Ito, Yoshihiko
description Asymmetric hydrosilylation of simple ketones with diphenylsilane proceeded at -40 °C in the presence of a rhodium complex (0.001—0.01 molar amount) coordinated with a trans-chelating chiral bisphosphine ligand bearing linear alkyl substituents on the phosphorus atoms, (R,R)-(S,S)-Et-, Pr-, or BuTRAP, giving the corresponding optically active (S)-secondary alcohols with up to 97% ee. The asymmetric hydrosilylation using TRAP ligands with bulkier P-substituents resulted in much lower enantioselectivities. The EtTRAP-rhodium catalyst was also effective for asymmetric hydrosilylation of keto esters with a coordination site for a rhodium atom (up to 98% ee). Optically active symmetrical diols were obtained with up to 99% ee from the corresponding diketones via the asymmetric reduction using 2.5 molar amounts of diphenylsilane.
doi_str_mv 10.1246/bcsj.73.485
format article
fullrecord <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_journals_1459461774</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>3130522351</sourcerecordid><originalsourceid>FETCH-LOGICAL-c443t-5c46088a41be47a001332b207e9e2a16b01125d7d30885dc9363abf1392d2ab23</originalsourceid><addsrcrecordid>eNptkMtOwzAQRS0EEqWw4gcssUQpfuW1LBVQRCUq0a4jJ3Fbl8QuHmeRH-F7cWgXLFjMjEY6c6_mInRLyYQykTyUFewnKZ-ILD5DI8pFFpGEi3M0IoTkEUtSfomuAPZhzWKRj9D3FPq2Vd7pCs_72lnQTd9Ir63BdoPflLdGAV6DNlu8ctJANNupAQj7bKedbPBShf7ZN6WGw86G0kbhhd5KUwN-VNIN7NLpVroeTwcSf3QleO07ZTzgYLX8vbOuAzz1toVrdLGRDaib0xyj9fPTajaPFu8vr7PpIqqE4D6KK5GQLJOClkqkkhDKOSsZSVWumKRJSShlcZ3WPFBxXeU84bLcUJ6zmsmS8TG6O-oenP3qFPhibztngmVBRZyLhKapCNT9kapCPuDUpjgcvykoKYbgiyH4IuVFCD7Q2YneqVZXQctWWvl-Lw_S_NH_5_QHfzWNhg</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1459461774</pqid></control><display><type>article</type><title>Asymmetric Hydrosilylation of Ketones Using Trans-Chelating Chiral Peralkylbisphosphine Ligands Bearing Primary Alkyl Substituents on Phosphorus Atoms</title><source>Oxford Journals Online</source><creator>Kuwano, Ryoichi ; Sawamura, Masaya ; Shirai, Junya ; Takahashi, Masatoshi ; Ito, Yoshihiko</creator><creatorcontrib>Kuwano, Ryoichi ; Sawamura, Masaya ; Shirai, Junya ; Takahashi, Masatoshi ; Ito, Yoshihiko</creatorcontrib><description>Asymmetric hydrosilylation of simple ketones with diphenylsilane proceeded at -40 °C in the presence of a rhodium complex (0.001—0.01 molar amount) coordinated with a trans-chelating chiral bisphosphine ligand bearing linear alkyl substituents on the phosphorus atoms, (R,R)-(S,S)-Et-, Pr-, or BuTRAP, giving the corresponding optically active (S)-secondary alcohols with up to 97% ee. The asymmetric hydrosilylation using TRAP ligands with bulkier P-substituents resulted in much lower enantioselectivities. The EtTRAP-rhodium catalyst was also effective for asymmetric hydrosilylation of keto esters with a coordination site for a rhodium atom (up to 98% ee). Optically active symmetrical diols were obtained with up to 99% ee from the corresponding diketones via the asymmetric reduction using 2.5 molar amounts of diphenylsilane.</description><identifier>ISSN: 0009-2673</identifier><identifier>EISSN: 1348-0634</identifier><identifier>DOI: 10.1246/bcsj.73.485</identifier><language>eng</language><publisher>Tokyo: The Chemical Society of Japan</publisher><ispartof>Bulletin of the Chemical Society of Japan, 2000-02, Vol.73 (2), p.485-496</ispartof><rights>The Chemical Society of Japan</rights><rights>Copyright Japan Science and Technology Agency 2000</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c443t-5c46088a41be47a001332b207e9e2a16b01125d7d30885dc9363abf1392d2ab23</citedby><cites>FETCH-LOGICAL-c443t-5c46088a41be47a001332b207e9e2a16b01125d7d30885dc9363abf1392d2ab23</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids></links><search><creatorcontrib>Kuwano, Ryoichi</creatorcontrib><creatorcontrib>Sawamura, Masaya</creatorcontrib><creatorcontrib>Shirai, Junya</creatorcontrib><creatorcontrib>Takahashi, Masatoshi</creatorcontrib><creatorcontrib>Ito, Yoshihiko</creatorcontrib><title>Asymmetric Hydrosilylation of Ketones Using Trans-Chelating Chiral Peralkylbisphosphine Ligands Bearing Primary Alkyl Substituents on Phosphorus Atoms</title><title>Bulletin of the Chemical Society of Japan</title><addtitle>Bulletin of the Chemical Society of Japan</addtitle><description>Asymmetric hydrosilylation of simple ketones with diphenylsilane proceeded at -40 °C in the presence of a rhodium complex (0.001—0.01 molar amount) coordinated with a trans-chelating chiral bisphosphine ligand bearing linear alkyl substituents on the phosphorus atoms, (R,R)-(S,S)-Et-, Pr-, or BuTRAP, giving the corresponding optically active (S)-secondary alcohols with up to 97% ee. The asymmetric hydrosilylation using TRAP ligands with bulkier P-substituents resulted in much lower enantioselectivities. The EtTRAP-rhodium catalyst was also effective for asymmetric hydrosilylation of keto esters with a coordination site for a rhodium atom (up to 98% ee). Optically active symmetrical diols were obtained with up to 99% ee from the corresponding diketones via the asymmetric reduction using 2.5 molar amounts of diphenylsilane.</description><issn>0009-2673</issn><issn>1348-0634</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2000</creationdate><recordtype>article</recordtype><recordid>eNptkMtOwzAQRS0EEqWw4gcssUQpfuW1LBVQRCUq0a4jJ3Fbl8QuHmeRH-F7cWgXLFjMjEY6c6_mInRLyYQykTyUFewnKZ-ILD5DI8pFFpGEi3M0IoTkEUtSfomuAPZhzWKRj9D3FPq2Vd7pCs_72lnQTd9Ir63BdoPflLdGAV6DNlu8ctJANNupAQj7bKedbPBShf7ZN6WGw86G0kbhhd5KUwN-VNIN7NLpVroeTwcSf3QleO07ZTzgYLX8vbOuAzz1toVrdLGRDaib0xyj9fPTajaPFu8vr7PpIqqE4D6KK5GQLJOClkqkkhDKOSsZSVWumKRJSShlcZ3WPFBxXeU84bLcUJ6zmsmS8TG6O-oenP3qFPhibztngmVBRZyLhKapCNT9kapCPuDUpjgcvykoKYbgiyH4IuVFCD7Q2YneqVZXQctWWvl-Lw_S_NH_5_QHfzWNhg</recordid><startdate>20000201</startdate><enddate>20000201</enddate><creator>Kuwano, Ryoichi</creator><creator>Sawamura, Masaya</creator><creator>Shirai, Junya</creator><creator>Takahashi, Masatoshi</creator><creator>Ito, Yoshihiko</creator><general>The Chemical Society of Japan</general><general>Chemical Society of Japan</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope></search><sort><creationdate>20000201</creationdate><title>Asymmetric Hydrosilylation of Ketones Using Trans-Chelating Chiral Peralkylbisphosphine Ligands Bearing Primary Alkyl Substituents on Phosphorus Atoms</title><author>Kuwano, Ryoichi ; Sawamura, Masaya ; Shirai, Junya ; Takahashi, Masatoshi ; Ito, Yoshihiko</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c443t-5c46088a41be47a001332b207e9e2a16b01125d7d30885dc9363abf1392d2ab23</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2000</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kuwano, Ryoichi</creatorcontrib><creatorcontrib>Sawamura, Masaya</creatorcontrib><creatorcontrib>Shirai, Junya</creatorcontrib><creatorcontrib>Takahashi, Masatoshi</creatorcontrib><creatorcontrib>Ito, Yoshihiko</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Bulletin of the Chemical Society of Japan</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kuwano, Ryoichi</au><au>Sawamura, Masaya</au><au>Shirai, Junya</au><au>Takahashi, Masatoshi</au><au>Ito, Yoshihiko</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Asymmetric Hydrosilylation of Ketones Using Trans-Chelating Chiral Peralkylbisphosphine Ligands Bearing Primary Alkyl Substituents on Phosphorus Atoms</atitle><jtitle>Bulletin of the Chemical Society of Japan</jtitle><addtitle>Bulletin of the Chemical Society of Japan</addtitle><date>2000-02-01</date><risdate>2000</risdate><volume>73</volume><issue>2</issue><spage>485</spage><epage>496</epage><pages>485-496</pages><issn>0009-2673</issn><eissn>1348-0634</eissn><abstract>Asymmetric hydrosilylation of simple ketones with diphenylsilane proceeded at -40 °C in the presence of a rhodium complex (0.001—0.01 molar amount) coordinated with a trans-chelating chiral bisphosphine ligand bearing linear alkyl substituents on the phosphorus atoms, (R,R)-(S,S)-Et-, Pr-, or BuTRAP, giving the corresponding optically active (S)-secondary alcohols with up to 97% ee. The asymmetric hydrosilylation using TRAP ligands with bulkier P-substituents resulted in much lower enantioselectivities. The EtTRAP-rhodium catalyst was also effective for asymmetric hydrosilylation of keto esters with a coordination site for a rhodium atom (up to 98% ee). Optically active symmetrical diols were obtained with up to 99% ee from the corresponding diketones via the asymmetric reduction using 2.5 molar amounts of diphenylsilane.</abstract><cop>Tokyo</cop><pub>The Chemical Society of Japan</pub><doi>10.1246/bcsj.73.485</doi><tpages>12</tpages></addata></record>
fulltext fulltext
identifier ISSN: 0009-2673
ispartof Bulletin of the Chemical Society of Japan, 2000-02, Vol.73 (2), p.485-496
issn 0009-2673
1348-0634
language eng
recordid cdi_proquest_journals_1459461774
source Oxford Journals Online
title Asymmetric Hydrosilylation of Ketones Using Trans-Chelating Chiral Peralkylbisphosphine Ligands Bearing Primary Alkyl Substituents on Phosphorus Atoms
url http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-02-12T09%3A28%3A04IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Asymmetric%20Hydrosilylation%20of%20Ketones%20Using%20Trans-Chelating%20Chiral%20Peralkylbisphosphine%20Ligands%20Bearing%20Primary%20Alkyl%20Substituents%20on%20Phosphorus%20Atoms&rft.jtitle=Bulletin%20of%20the%20Chemical%20Society%20of%20Japan&rft.au=Kuwano,%20Ryoichi&rft.date=2000-02-01&rft.volume=73&rft.issue=2&rft.spage=485&rft.epage=496&rft.pages=485-496&rft.issn=0009-2673&rft.eissn=1348-0634&rft_id=info:doi/10.1246/bcsj.73.485&rft_dat=%3Cproquest_cross%3E3130522351%3C/proquest_cross%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-c443t-5c46088a41be47a001332b207e9e2a16b01125d7d30885dc9363abf1392d2ab23%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_pqid=1459461774&rft_id=info:pmid/&rfr_iscdi=true