eprintid: 19475
rev_number: 22
userid: 1418
dir: disk0/00/01/94/75
datestamp: 2013-07-31 17:45:34
lastmod: 2021-06-12 22:56:28
status_changed: 2013-07-31 17:45:34
type: article
metadata_visibility: show
item_issues_count: 0
eprint_status: archive
creators_name: Manku, S
creators_name: Curran, DP
creators_email: 
creators_email: curran@pitt.edu
creators_id: 
creators_id: CURRAN
title: Fluorous mixture synthesis of 4-alkylidene cyclopentenones via a rhodium-catalyzed [2+2+1] cycloaddition of alkynyl allenes
ispublished: pub
divisions: sch_as_chemistry
full_text_status: public
abstract: Fluorous mixture synthesis was used to prepare a library of 4-alkylidene cyclopentenones starting from a mixture of four α-amino acid derivatives tagged with different fluorous benzyl carbamates (FCBz) of varying fluorine content. The amino acids were converted to the corresponding propargyl esters and then subjected to an ester-enolate Claisen rearrangement to give a mixture of allenic amino esters. The allenes were then split four ways and propargylated with different propargyl bromides to give four mixtures of alkynyl allenes. The 4-alkylidene cyclopentenones were formed by a formal [2+2+1] cycloaddition of the alkynyl allenes using catalytic [Rh(CO)2Cl] 2 under CO atmosphere. Demixing by fluorous preparative HPLC, removal of the fluorous benzyl carbamates, and then exposure to HCl/ether gave the hydrochloride salts of 16 compounds as diastereomeric mixtures in 69-99% purity. Thus, after just 26 chemical steps, a library of 16 cyclopentenones was prepared by using fluorous mixture synthesis. By comparison, the same library would have required 112 steps if each compound were made individually by parallel synthesis.
date: 2005-01-01
date_type: published
publication: Journal of Combinatorial Chemistry
volume: 7
number: 1
pagerange: 63 - 68
refereed: TRUE
issn: 1520-4766
id_number: 10.1021/cc049899x
pmid: 15638481
mesh_headings: Alkadienes--chemistry
mesh_headings: Alkaloids--chemistry
mesh_headings: Catalysis
mesh_headings: Chromatography, High Pressure Liquid
mesh_headings: Combinatorial Chemistry Techniques
mesh_headings: Cyclopentanes--chemical synthesis
mesh_headings: Cyclopentanes--chemistry
mesh_headings: Fluorine--chemistry
mesh_headings: Magnetic Resonance Spectroscopy
mesh_headings: Molecular Structure
mesh_headings: Rhodium--chemistry
chemical_names: Alkadienes
chemical_names: Alkaloids
chemical_names: Cyclopentanes
chemical_names: propadiene
chemical_names: tecomine
chemical_names: Rhodium
chemical_names: Fluorine
chemical_names: cyclopentenone
citation:   Manku, S and Curran, DP  (2005) Fluorous mixture synthesis of 4-alkylidene cyclopentenones via a rhodium-catalyzed [2+2+1] cycloaddition of alkynyl allenes.  Journal of Combinatorial Chemistry, 7 (1).  63 - 68.  ISSN 1520-4766     
document_url: http://d-scholarship-dev.library.pitt.edu/19475/1/licence.txt