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rdf:type |
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lifeskim:mentions |
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pubmed:issue |
3
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pubmed:dateCreated |
2009-1-21
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pubmed:abstractText |
The lack of methods for the stereoselective transfer of functionalized carbenoids is one of the most significant deficiencies of Simmons-Smith cyclopropanation reactions. Outlined herein are one-pot methods for the catalytic asymmetric synthesis of halocyclopropyl alcohols with up to four stereogenic centers from achiral starting materials. The first method involves asymmetric alkyl addition to a conjugated enal to generate an allylic alkoxide followed by tandem diastereoselective iodo-, bromo-, or chlorocyclopropanation to furnish halocyclopropyl alcohols. Enantioselectivities in these processes range from 89-99%, and dr's of >20:1 were achieved with all substrates optimized. The second method consists of an asymmetric vinylation of a saturated or aromatic aldehyde followed by a diastereoselective iodocyclopropanation to produce iodocyclopropyl alcohols with enantioselectivities between 86 and 99% and dr's of >20:1. These complementary methods enable the efficient synthesis of a variety of halocyclopropyl alcohols in one-pot procedures. Preliminary efforts to functionalize iodocyclopropanes involve reaction with an excess of LiCu(n-Bu)(2) to generate the cyclopropyl cuprate. This intermediate can be quenched with allyl bromides to generate the allylated cyclopropyl alcohols without loss of enantio- or diastereoselectivity.
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pubmed:grant |
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pubmed:commentsCorrections |
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-11674024,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-11734015,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-11792203,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-11952363,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-12371863,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-12452703,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-12683775,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-12683776,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-12683792,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-12940753,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-14599180,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-15493905,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-15704959,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-16173729,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-16173730,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-16231920,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-16594699,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-17622181,
http://linkedlifedata.com/resource/pubmed/commentcorrection/19154172-18085796
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pubmed:language |
eng
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pubmed:journal |
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pubmed:citationSubset |
IM
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pubmed:chemical |
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pubmed:status |
MEDLINE
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pubmed:month |
Jan
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pubmed:issn |
1520-5126
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pubmed:author |
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pubmed:issnType |
Electronic
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pubmed:day |
28
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pubmed:volume |
131
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pubmed:owner |
NLM
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pubmed:authorsComplete |
Y
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pubmed:pagination |
954-62
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pubmed:dateRevised |
2011-9-26
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pubmed:meshHeading |
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pubmed:year |
2009
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pubmed:articleTitle |
Highly enantio- and diastereoselective one-pot methods for the synthesis of halocyclopropyl alcohols.
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pubmed:affiliation |
P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
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pubmed:publicationType |
Journal Article,
Research Support, U.S. Gov't, Non-P.H.S.,
Research Support, N.I.H., Extramural
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