Co-reporter:Thomas P. Bobinski, Philip L. Fuchs
Tetrahedron Letters 2015 Volume 56(Issue 28) pp:4155-4158
Publication Date(Web):8 July 2015
DOI:10.1016/j.tetlet.2015.04.098
Co-reporter:Thomas P. Bobinski, Philip L. Fuchs
Tetrahedron Letters 2015 Volume 56(Issue 28) pp:4151-4154
Publication Date(Web):8 July 2015
DOI:10.1016/j.tetlet.2015.05.044
The first broad catalytic dihydroxylation of enantiopure cyclic vinyl sulfones followed by oxidative cleavage of the resulting acyloin provides linear termini-differentiated polyketide fragments. This mild vinyl sulfone cleavage provides an effective alternative to the current ozonolysis protocol.
Co-reporter:Ananda Kumar Kanduluru, Prabal Banerjee, John A Beutler, and Philip L Fuchs
The Journal of Organic Chemistry 2013 Volume 78(Issue 18) pp:9085-9092
Publication Date(Web):July 30, 2013
DOI:10.1021/jo401171q
The convergent synthesis of 25-epi ritterostatin GN1N is described for the first time, starting from hecogenin acetate (HA). Stereoselective dihydroxylation employing the chiral ligand (DHQ)2PHAL was used as the key step to introduce the C25 epi-stereocenter on the north 1 segment. The title compound was obtained through a coupling reaction between the C3-keto-azide (cstat North 1) and North G.
Co-reporter:G. Reza Ebrahimian, Xavier Mollat du Jourdin, and Philip L. Fuchs
Organic Letters 2012 Volume 14(Issue 10) pp:2630-2633
Publication Date(Web):April 30, 2012
DOI:10.1021/ol300996m
A Jacobsen epoxidation protocol using H2O2 as oxidant was designed for the large-scale preparation of various epoxy vinyl sulfones. A number of cocatalysts were screened, and pH control led to increased reaction rate, higher turnover number, and improved reliability.
Co-reporter:Vikas Sikervar, James C. Fleet and Philip L. Fuchs
Chemical Communications 2012 vol. 48(Issue 72) pp:9077-9079
Publication Date(Web):01 Aug 2012
DOI:10.1039/C2CC33054G
A synthesis of enantiopure 19-nor-Vitamin D3 and its C-2 substituted cyclic phosphate analogs is achieved via in situ trapping of an α-sulfonyl anion with a CD-ring allyl chloride and 1,2-eliminative desulfonylation exploiting the basic properties of TBAF. The A-ring is prepared via anti-selective dithiane addition to vinyl sulfone and LiBH4 mediated sequential bis reduction of an epoxy vinyl sulfone.
Co-reporter:Vikas Sikervar and Philip L. Fuchs
Organic Letters 2012 Volume 14(Issue 11) pp:2922-2924
Publication Date(Web):May 16, 2012
DOI:10.1021/ol301144a
Alcohol-directed intramolecular methylation of an enantiopure allyl sulfone using AlMe3 provides a trans-hydrindane CD ring alcohol. The substrate cis-CD ring allyl sulfone alcohol is prepared via intramolecular allyl sulfonyl anion addition to aldehyde using Ba(OH)2.
Co-reporter:Vikas Sikervar, James C. Fleet, and Philip L. Fuchs
The Journal of Organic Chemistry 2012 Volume 77(Issue 11) pp:5132-5138
Publication Date(Web):April 25, 2012
DOI:10.1021/jo300672a
A coupling strategy for the synthesis of 2,4-dimethyl-1α,25(OH)2D3 is achieved which involves methylation of a pro-A ring vinyl sulfone and in situ traping of the allyl sulfonyl anion with a CD ring allyl chloride. TBAF-promoted 1,2-eliminative desulfonylation and concomitant silyl ether deprotection gives the vitamin D3 analogue.
Co-reporter:Wan Pyo Hong, Mohammad N. Noshi, Ahmad El-Awa, and Philip L. Fuchs
Organic Letters 2011 Volume 13(Issue 24) pp:6342-6345
Publication Date(Web):November 22, 2011
DOI:10.1021/ol2024746
The synthesis of C1–C20 and C15–C27 segments of Aplyronine A is described. Oxidative cleavage of cyclic vinyl sulfones has been used to prepare key fragments of Aplyronine A. Key precursors are united by Horner–Wadsworth–Emmons and Julia–Kociensky olefination for the respective elaboration of the C1–C20 and C15–C27 segments.
Co-reporter:Madduri Srinivasarao, Taesik Park, Yuzhong Chen and Philip L. Fuchs
Chemical Communications 2011 vol. 47(Issue 20) pp:5858-5860
Publication Date(Web):18 Apr 2011
DOI:10.1039/C1CC11448D
A stereoselective synthesis of the apoptolidin disaccharide is reported. The key chemistry features a new transformation utilizing a highly selective tetramethylalkoxyalanate[V]-directedsyn-methylation of a vinylogous ester, isolation of a hydrate of a 2-keto sugar, an eco-friendly radical cleavage of a bromomethyl group, and an efficient preparation of a fluorodisaccharidevia the use of XtalFluor-E.
Co-reporter:Kanduluru Ananda Kumar, James J. La Clair, and Philip L. Fuchs
Organic Letters 2011 Volume 13(Issue 19) pp:5334-5337
Publication Date(Web):September 14, 2011
DOI:10.1021/ol202139z
The cephalostatin and ritterazine natural products comprise a potent family of bis-steroidal pyrazines that display potent single-digit nanomolar inhibition of tumor cell growth. An active fluorescent ritterazine–cephalostatin hybrid probe was developed using detailed SAR data derived through total synthetic efforts. A combination of time course and confocal imaging studies indicate that this natural product family is rapidly taken up in tumor cells and localizes subcellularly within ER and surrounding the nuclear–ER interface.
Co-reporter:Vikas Sikervar and Philip L. Fuchs
Chemical Communications 2011 vol. 47(Issue 12) pp:3472-3474
Publication Date(Web):09 Feb 2011
DOI:10.1039/C0CC05405D
Dimethylsulfonium methylide undergoes SN2′ addition/1,2-elimination with epoxy vinyl sulfones to generate enantiopure six and seven membered cross-conjugated hydroxy vinyl sulfones. Moderate to excellent yields were obtained for both six and seven membered substrates.
Co-reporter:Madduri Srinivasarao, Youngsoon Kim, Xiaojin Harry Li, Daniel W. Robbins, and Philip L. Fuchs
The Journal of Organic Chemistry 2011 Volume 76(Issue 19) pp:7834-7841
Publication Date(Web):August 9, 2011
DOI:10.1021/jo200934w
Synthesis of a C1–C27 fragment, a key intermediate in the synthesis of apoptolidin D, is reported. The synthesis involves a combination of Heck coupling and Horner–Wadsworth–Emmons reaction for the C1–C7 trienoate portion and an efficient Suzuki cross-coupling protocol for the C10–C13 diene portion.
Co-reporter:Seongmin Lee, Thomas G. LaCour and Philip L. Fuchs
Chemical Reviews 2009 Volume 109(Issue 6) pp:2275
Publication Date(Web):May 13, 2009
DOI:10.1021/cr800365m
Co-reporter:Ahmad El-Awa, Mohammad N. Noshi, Xavier Mollat du Jourdin and Philip L. Fuchs
Chemical Reviews 2009 Volume 109(Issue 6) pp:2315
Publication Date(Web):May 13, 2009
DOI:10.1021/cr800309r
Co-reporter:Wan Pyo Hong ; Ahmad El-Awa ;Philip L. Fuchs
Journal of the American Chemical Society 2009 Volume 131(Issue 26) pp:9150-9151
Publication Date(Web):June 17, 2009
DOI:10.1021/ja9017557
Methods have been developed for regio- and stereoselective 1,4-syn or 1,4-anti methylation of seven-membered epoxyvinylsulfones. 1,4-Syn addition is achieved via the combination of Me2Zn and catalytic Li2CuCl4, a hitherto unexplored reagent combination. The complementary 1,4-anti addition relies on Cu(I) catalyzed methyl Grignard addition or (CH3)3Al assisted CH3Cu addition. The methods described were assayed on four diastereomeric stereodiads and on their parent epoxide.
Co-reporter:Eduardo Torres;Yuzhong Chen;In Chul Kim;P. L. Fuchs
Angewandte Chemie International Edition 2003 Volume 42(Issue 27) pp:
Publication Date(Web):10 JUL 2003
DOI:10.1002/anie.200350955
Getting the most out of sulfur. Enantiopure epoxyvinyl sulfone 1 is transformed to syn- and anti-dienyl sulfones 2 and 3, respectively, by means of a nucleophilic methylation/sulfenylation/directed elimination reaction sequence. Compound 2 has been converted into termini-differentiated seven-carbon polypropionate segments found in five biologically significant natural products.
Co-reporter:Eduardo Torres;Yuzhong Chen;In Chul Kim;P. L. Fuchs
Angewandte Chemie 2003 Volume 115(Issue 27) pp:
Publication Date(Web):10 JUL 2003
DOI:10.1002/ange.200350955
Bestleistungen dank Schwefel: Durch eine Reaktionssequenz aus nucleophiler Methylierung, Sulfenylierung und Eliminierung wird das enantiomerenreine Epoxyvinylsulfon 1 in die syn- oder anti-Dienylsulfide 2 bzw. 3 umgewandelt. Das vielseitige Intermediat 2 kann auch als siebenatomiges Synthon für die Polypropionat-Einheiten von fünf wichtigen Naturstoffen verwendet werden.
Co-reporter:Madduri Srinivasarao, Taesik Park, Yuzhong Chen and Philip L. Fuchs
Chemical Communications 2011 - vol. 47(Issue 20) pp:NaN5860-5860
Publication Date(Web):2011/04/18
DOI:10.1039/C1CC11448D
A stereoselective synthesis of the apoptolidin disaccharide is reported. The key chemistry features a new transformation utilizing a highly selective tetramethylalkoxyalanate[V]-directedsyn-methylation of a vinylogous ester, isolation of a hydrate of a 2-keto sugar, an eco-friendly radical cleavage of a bromomethyl group, and an efficient preparation of a fluorodisaccharidevia the use of XtalFluor-E.
Co-reporter:Vikas Sikervar, James C. Fleet and Philip L. Fuchs
Chemical Communications 2012 - vol. 48(Issue 72) pp:NaN9079-9079
Publication Date(Web):2012/08/01
DOI:10.1039/C2CC33054G
A synthesis of enantiopure 19-nor-Vitamin D3 and its C-2 substituted cyclic phosphate analogs is achieved via in situ trapping of an α-sulfonyl anion with a CD-ring allyl chloride and 1,2-eliminative desulfonylation exploiting the basic properties of TBAF. The A-ring is prepared via anti-selective dithiane addition to vinyl sulfone and LiBH4 mediated sequential bis reduction of an epoxy vinyl sulfone.
Co-reporter:Vikas Sikervar and Philip L. Fuchs
Chemical Communications 2011 - vol. 47(Issue 12) pp:NaN3474-3474
Publication Date(Web):2011/02/09
DOI:10.1039/C0CC05405D
Dimethylsulfonium methylide undergoes SN2′ addition/1,2-elimination with epoxy vinyl sulfones to generate enantiopure six and seven membered cross-conjugated hydroxy vinyl sulfones. Moderate to excellent yields were obtained for both six and seven membered substrates.
![Serine,N,N,O-trimethyl-,(3E,5E,8R,9S,10R,11R,14S,15E,18R,20R,21E,24S)-24-[(1S,2S,3S,6R,7S,8R,9R,10E)-8-(acetyloxy)-6-[2-(dimethylamino)-1-oxopropoxy]-11-(formylmethylamino)-2-hydroxy-1,3,7,9-tetramethyl-10-undecen-1-yl]-10-hydroxy-14,20-dimethoxy-9,11,15,18-tetramethyl-2-oxooxacyclotetracosa-3,5,15,21-tetraen-8-ylester](http://img.cochemist.com/ccimg/152000/151923-84-1.png)
![Serine,N,N,O-trimethyl-,(3E,5E,8R,9S,10R,11R,14S,15E,18R,20R,21E,24S)-24-[(1S,2S,3S,6R,7S,8R,9R,10E)-8-(acetyloxy)-6-[2-(dimethylamino)-1-oxopropoxy]-11-(formylmethylamino)-2-hydroxy-1,3,7,9-tetramethyl-10-undecen-1-yl]-10-hydroxy-14,20-dimethoxy-9,11,15,18-tetramethyl-2-oxooxacyclotetracosa-3,5,15,21-tetraen-8-ylester](http://img.cochemist.com/ccimg/152000/151923-84-1_b.png)
![8-OXABICYCLO[5.1.0]OCT-2-ENE, 2-(PHENYLSULFONYL)-, (1R,7R)-](http://img.cochemist.com/ccimg/773200/773148-44-0.png)
![8-OXABICYCLO[5.1.0]OCT-2-ENE, 2-(PHENYLSULFONYL)-, (1R,7R)-](http://img.cochemist.com/ccimg/773200/773148-44-0_b.png)
