Simon J. Meek

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Name: Meek, Simon

Organization: The University of North Carolina at Chapel Hill , USA

Department: Department of Chemistry

Title: Assistant Professor(PhD)

TOPICS

Inorganic Chemistry

Chemicals
References

Stereoselective Tandem Bis-Electrophile Couplings of Diborylmethane

Co-reporter:Stephanie A. Murray, Michael Z. Liang, and Simon J. Meek

Journal of the American Chemical Society October 11, 2017 Volume 139(Issue 40) pp:14061-14061

Publication Date(Web):September 21, 2017

DOI:10.1021/jacs.7b09309

A copper-catalyzed three-component linchpin coupling method for the stereoselective union of readily available epoxides and allyl electrophiles is disclosed. Transformations employ [B(pin)]2-methane as a conjunctive reagent, resulting in the formation of two C–C bonds at a single carbon center bearing a C(sp3) organoboron functional group. Products are obtained in 42–99% yield, and up to >20:1 dr. The utility of the approach is highlighted by stereospecific transformations entailing allylation, tandem cross coupling, and application to the synthesis 1,3-polyol motifs.

Chiral Pincer Carbodicarbene Ligands for Enantioselective Rhodium-Catalyzed Hydroarylation of Terminal and Internal 1,3-Dienes with Indoles

Co-reporter:Justin S. Marcum, Courtney C. Roberts, Rajith S. Manan, Tia N. Cervarich, and Simon J. Meek

Journal of the American Chemical Society November 8, 2017 Volume 139(Issue 44) pp:15580-15580

Publication Date(Web):October 23, 2017

DOI:10.1021/jacs.7b08575

Catalytic enantioselective addition of N-heteroarenes to terminal and internal 1,3-dienes is reported. Reactions are promoted by 5 mol % of Rh catalyst supported by a new chiral pincer carbodicarbene ligand that delivers allylic substituted arenes in up to 95% yield and up to 98:2 er. Mechanistic and X-ray evidence is presented that supports that the reaction proceeds via a Rh(III)-η3-allyl.

Enantio- and Diastereoselective Synthesis of Hydroxy Bis(boronates) via Cu-Catalyzed Tandem Borylation/1,2-Addition

Co-reporter:Jacob C. Green, Matthew V. Joannou, Stephanie A. Murray, Joseph M. Zanghi, and Simon J. Meek

ACS Catalysis July 7, 2017 Volume 7(Issue 7) pp:4441-4441

Publication Date(Web):May 25, 2017

DOI:10.1021/acscatal.7b01123

Catalytic enantioselective synthesis of 1-hydroxy-2,3-bisboronate esters through multicomponent borylation/1,2-addition is reported. Catalyst and substrates are readily available, form both a C–B and C–C bond, and generate up to three contiguous stereocenters. The reaction is tolerant of aryl, vinyl, and alkyl aldehydes and ketones in up to 95% yield, >20:1 dr, and 99:1 er. Intramolecular additions to aldehydes and ketones result in stereodivergent processes. The hydroxy bis(boronate) ester products are amenable to site-selective chemical elaboration.Keywords: Cu-catalyzed; tandem borylation;

Diastereoselective Synthesis of γ-Substituted 2-Butenolides via (CDC)-Rh-Catalyzed Intermolecular Hydroalkylation of Dienes with Silyloxyfurans

Co-reporter:Matthew J. Goldfogel, Courtney C. Roberts, Rajith S. Manan, and Simon J. Meek

Organic Letters 2017 Volume 19(Issue 1) pp:90-93

Publication Date(Web):December 20, 2016

DOI:10.1021/acs.orglett.6b03369

Catalytic intermolecular hydroalkylation of dienes with silyloxyfuran nucleophiles is reported. Reactions are catalyzed by 5 mol % of a (CDC)-Rh complex and proceed in up to 87% yield and 6:1 dr (syn/anti) to provide allylic butenolides bearing vicinal stereocenters. Reactions proceed with terminal aryl and alkyl dienes and with modified silyl enol ether nucleophiles including a thiophenone variant. Utility of the products is demonstrated in the synthesis of a polypropionate anti,syn-stereotriad.

Diastereoselective synthesis of vicinal tertiary and N-substituted quaternary stereogenic centers by catalytic hydroalkylation of dienes

Co-reporter:Matthew J. Goldfogel and Simon J. Meek

Chemical Science 2016 vol. 7(Issue 7) pp:4079-4084

Publication Date(Web):11 Mar 2016

DOI:10.1039/C5SC04908C

An efficient and diastereoselective (CDC)–Rh-catalyzed hydroalkylation of dienes with 1,3-oxazol-5(4H)-ones is reported. Aryl and alkyl substituted dienes are converted to α,α-substituted oxazolones (24 examples) by the formation of N-substituted quaternary carbon stereogenic centers in good yields (up to 96%) and with high diastereoselectivity (>20:1 dr). The reaction is tolerant of a range of dienes and oxazolones bearing various functional groups. Utility of the oxazolone products is illustrated through hydrolysis to form α,β-substituted α-amino acid analogues and stereoselective epoxidation of the resultant alkene to create four contiguous stereocenters.

Enantio- and Diastereoselective 1,2-Additions to -Ketoesters with Diborylmethane and Substituted 1,1-Diborylalkanes

Co-reporter:Stephanie A. Murray;Jacob C. Green;Sanita B. Tailor ; Simon J. Meek

Angewandte Chemie 2016 Volume 128( Issue 31) pp:9211-9215

Publication Date(Web):

DOI:10.1002/ange.201603465

Abstract

The catalytic enantioselective synthesis of boronate-substituted tertiary alcohols through additions of diborylmethane and substituted 1,1-diborylalkanes to α-ketoesters is reported. The reactions are catalyzed by readily available chiral phosphine/copper(I) complexes and produce β-hydroxyboronates containing up to two contiguous stereogenic centers in up to 99:1 e.r. and greater than 20:1 d.r. The utility of the organoboron products is demonstrated through several chemoselective functionalizations. Evidence indicates the reactions occur via an enantioenriched α-boryl-copper-alkyl intermediate.

Enantio- and Diastereoselective 1,2-Additions to -Ketoesters with Diborylmethane and Substituted 1,1-Diborylalkanes

Co-reporter:Stephanie A. Murray;Jacob C. Green;Sanita B. Tailor ; Simon J. Meek

Angewandte Chemie International Edition 2016 Volume 55( Issue 31) pp:9065-9069

Publication Date(Web):

DOI:10.1002/anie.201603465

Abstract

Enantio- and Diastereoselective Synthesis of 1,2-Hydroxyboronates through Cu-Catalyzed Additions of Alkylboronates to Aldehydes

Co-reporter:Matthew V. Joannou; Brandon S. Moyer

Journal of the American Chemical Society 2015 Volume 137(Issue 19) pp:6176-6179

Publication Date(Web):April 23, 2015

DOI:10.1021/jacs.5b03477

The first catalytic enantio- and diastereoselective synthesis of 1,2-hydroxyboronates is reported. Reactions are promoted by a readily available chiral monodentate phosphoramidite–copper complex in the presence of an alkyl 1,1-diboron reagent. Products contain two contiguous stereogenic centers and are obtained in up to 91% yield, >98:2 d.r., and 98:2 e.r. The reaction is tolerant of aryl and vinyl aldehydes, and the 1,2-hydroxyboronate products can be transformed into versatile derivatives. Mechanistic experiments indicate control of absolute stereochemistry of the α-boryl component.

Lewis Acid Activation of Carbodicarbene Catalysts for Rh-Catalyzed Hydroarylation of Dienes

Co-reporter:Courtney C. Roberts; Desirée M. Matías; Matthew J. Goldfogel

Journal of the American Chemical Society 2015 Volume 137(Issue 20) pp:6488-6491

Publication Date(Web):May 11, 2015

DOI:10.1021/jacs.5b03510

The activation of carbodicarbene (CDC)–Rh(I) pincer complexes by secondary binding of metal salts is reported for the catalytic site-selective hydro-heteroarylation of dienes (up to 98% yield and >98:2 γ:α). Reactions are promoted by 5 mol % of a readily available tridentate (CDC)–Rh complex in the presence of an inexpensive lithium salt. The reaction is compatible with a variety of terminal and internal dienes and tolerant of ester, alkyl halide, and boronate ester functional groups. X-ray data and mechanistic experiments provide support for the role of the metal salts on catalyst activation and shed light on the reaction mechanism. The increased efficiency (120 to 22 °C) made available by catalytic amounts of metal salts to catalysts containing C(0) donors is a significant aspect of the disclosed studies.

Silver(I)-Catalyzed Diastereoselective Synthesis of anti-1,2-Hydroxyboronates

Co-reporter:Matthew V. Joannou;Bron S. Moyer;Matthew J. Goldfogel ; Simon J. Meek

Angewandte Chemie International Edition 2015 Volume 54( Issue 47) pp:14141-14145

Publication Date(Web):

DOI:10.1002/anie.201507171

Abstract

A catalytic protocol for the diastereoselective synthesis of anti-1,2-hydroxyboronates is described. The process provides access to secondary alkyl organoborons. The deborylative 1,2-addition reactions of alkyl 1,1-diborons proceed in the presence of a silver(I) salt with either KOtBu or nBuLi as an activator. The catalytic diastereoselective protocol can be extended to aryl, alkenyl, and alkyl aldehydes with up to 99:1 d.r.

Silver(I)-Catalyzed Diastereoselective Synthesis of anti-1,2-Hydroxyboronates

Co-reporter:Matthew V. Joannou;Bron S. Moyer;Matthew J. Goldfogel ; Simon J. Meek

Angewandte Chemie 2015 Volume 127( Issue 47) pp:14347-14351

Publication Date(Web):

DOI:10.1002/ange.201507171

Abstract

Intermolecular Hydroamination of 1,3-Dienes Catalyzed by Bis(phosphine)carbodicarbene–Rhodium Complexes

Co-reporter:Matthew J. Goldfogel ; Courtney C. Roberts

Journal of the American Chemical Society 2014 Volume 136(Issue 17) pp:6227-6230

Publication Date(Web):April 17, 2014

DOI:10.1021/ja502275w

A carbodicarbene (CDC)-based pincer ligand scaffold is reported, along with its application to site-selective Rh(I)-catalyzed intermolecular hydroamination of 1,3-dienes with aryl and alkyl amines. To the best of our knowledge, this is the first example of the use of a well-defined CDC complex as an efficient catalyst. Transformations proceed in the presence of 1.0–5.0 mol % Rh complex at 35–120 °C; allylic amines are obtained in up to 97% yield and with >98:2 site selectivity.

Diastereoselective synthesis of vicinal tertiary and N-substituted quaternary stereogenic centers by catalytic hydroalkylation of dienes

Co-reporter:Matthew J. Goldfogel and Simon J. Meek

Chemical Science (2010-Present) 2016 - vol. 7(Issue 7) pp:NaN4084-4084

Publication Date(Web):2016/03/11

DOI:10.1039/C5SC04908C