Asymmetric Allylboration of Acyl Imines Catalyzed by Chiral Diols - PowerPoint PPT Presentation

Asymmetric Allylboration of Acyl Imines Catalyzed by Chiral Diols Sha Lou, Philip N. Moquist, Scott E. Schaus J. Am. Chem. Soc. ASAP Current literature Group Meeting Novembar, 24 th 2007 Filip Petronijevic Filip Petronijevic @ Wipf Group 1 2/17/2008

Chiral homoallylic amines as building blocks in sythesis Synthesis , 2005 , 2815. Org. Lett. 2000 , 2(13) , 1847. J. Am. Chem. Soc. 1990 , 112 . Filip Petronijevic @ Wipf Group 2 2/17/2008

Allyl Addition to the C=N bond Chiral allyl metal reagents: • allyl silanes • allyl boronates and boranes • diastereoselective allyl metal additions to chiral imines (Cu, Zn, Zr, Pd, In mediated additions) Stereochemistry Filip Petronijevic @ Wipf Group 3 2/17/2008

Allyl Silanes as Chiral Allylation Reagents Mechanism: coordination of both imine nitrogen and acyl oxigen with Lewis Acidic silane J. Am. Chem. Soc. 2003 , 125 , 9596. J. Am. Chem. Soc. 2004 , 126 , 5686. Filip Petronijevic @ Wipf Group 4 2/17/2008

Allylboranes: Addition to C=N Bond “9-BBDs contain a nearly ideal chiral pocket for the highly enantioselective allylation…” J. Am. Chem. Soc. 2006 , 128 , 8712. Filip Petronijevic @ Wipf Group 5 2/17/2008

Asymmetric Allylboration of Cyclic Imines: BINOL Starring Proposed transition states J. Amer. Chem. Soc. 2006 , 128 , 9646. Filip Petronijevic @ Wipf Group 6 2/17/2008

α - Aminoallylation of Aldehydes with Ammonia J. Am. Chem.Soc. 2004 , 126 , 7182. Filip Petronijevic @ Wipf Group 7 2/17/2008

Zinc vs . Boron: Opposing Modes of Stereocontrol Depending on Chelation Synlett , 2002 , 651. Filip Petronijevic @ Wipf Group 8 2/17/2008

Title Paper: Asymmetric Allylboration of Acyl Imines J. Am. Chem. Soc. ASAP Filip Petronijevic @ Wipf Group 9 2/17/2008

Asymmetric Allylboration of Acyl Imines: Solvent and Additive Effects J. Am. Chem. Soc. ASAP Filip Petronijevic @ Wipf Group 10 2/17/2008

Asymmetric Allylboration of Benzoyl Imines: Scope and Limitations J. Am. Chem. Soc. ASAP Filip Petronijevic @ Wipf Group 11 2/17/2008

Asymmetric Allylboration of Benzoyl Imines: What About Other Types of Imines? J. Am. Chem. Soc. ASAP Filip Petronijevic @ Wipf Group 12 2/17/2008

Crotylboration of Acyl Imines Removal of the N -Benzoyl Group: J. Am. Chem. Soc. ASAP Filip Petronijevic @ Wipf Group 13 2/17/2008

Mechanistic Studies: Boronate Ligand Exchange Allylboronates are activated via exchange of the alkoxy boronate ligands: • Using pinacol, ethylene glycol and 1,3-propanediol suffers from very slow reaction, low yields and stereoselectivity • Diisopropoxy boronate gave best results O O O O B O B O B O B O • The diol functionality of the catalyst is essential J. Am. Chem. Soc. ASAP Filip Petronijevic @ Wipf Group 14 2/17/2008

Mechanistic Studies: Spectroscopic Characterization of the Reaction J. Am. Chem. Soc. ASAP Filip Petronijevic @ Wipf Group 15 2/17/2008

Enantiofacial Selectivity in Asymmetric Allylboration: Proposed Transition States J. Am. Chem. Soc. ASAP Filip Petronijevic @ Wipf Group 16 2/17/2008

Conclusions • Highly enantioselective allylboration of acyl imines catalysed by chiral BINOL-derived catalysts has developed • The reaction is highly selective for both aryl and aliphatic acyl imines • Crotyl boronates give the corresponding anti -products in high diasteroselectivity • Mechanistic studies confirm ligand exchange between boronate and catalyst Filip Petronijevic @ Wipf Group 17 2/17/2008

Asymmetric Allylboration of Acyl Imines Catalyzed by Chiral Diols - PowerPoint PPT Presentation

Asymmetric Allylboration of Acyl Imines Catalyzed by Chiral Diols Sha Lou, Philip N. Moquist, Scott E. Schaus J. Am. Chem. Soc. ASAP Current literature Group Meeting Novembar, 24 th 2007 Filip Petronijevic Filip Petronijevic @ Wipf Group 1

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Asymmetric Allylboration of Acyl Imines Catalyzed by Chiral Diols - PowerPoint PPT Presentation

Asymmetric Allylboration of Acyl Imines Catalyzed by Chiral Diols Sha Lou, Philip N. Moquist, Scott E. Schaus J. Am. Chem. Soc. ASAP Current literature Group Meeting Novembar, 24 th 2007 Filip Petronijevic Filip Petronijevic @ Wipf Group 1

Enantioselective Total Synthesis of (+)-Homochelidonine by a Pd II - Catalyzed Asymmetric

Untargeted metabolomics reveals specific withanolides and fatty acyl glycoside as tentative

Symmetric and Asymmetric Key Cryptography(Part 2) By Radhika B S Contents Asymmetric Key

modulated by histone modifications modifications are catalyzed by enzymes alterations

Medium-chain acyl-CoA dehydrogenase deficiency occurs in around 1/15,000 births 1,2

ISCOC-15 Poster Presentation No. Name Title OP-01 Yi-En Liang Palladium-Catalyzed

Copper-Catalyzed Reaction of Alkyl Halides with Cyclopentadienylmagnesium Reagent 1) cat. Cu(OTf)

Overview What is an Asymmetric Barrier? Median barrier with unbalanced roadway elevations

Construction of Tetrahydrofurans by Pd(II)/Pd(IV) - Catalyzed Aminooxygenation of Alkenes Desai,

via Hgershoff reaction or Cu catalyzed intramolecular C-S bond formation Damien Hdou 1 ,

Highly turnover number cyanosilylation of carbonyl compounds catalyzed by tetraethylammonium 2-

Pd Catalyzed Domino Alkyne Dimerization/Double [2+2] Allenyne Cycloaddition Benito Alcaide,

Systematic study of lipase-catalyzed resolution of propranolol precursors Isabel

Synthesis of Zinc Oxide Catalyzed David Kisailus by Silicatein and Biomimetic SAMs Faculty

Selenium catalyzed oxidation of alkynes in aqueous media Claudio Santi*, Benedetta Battistelli,

Oxidation of Aromatic Alcohols Catalyzed by Non-Heme Iron Amido Complexes Takafumi Shanoh, 1,2

Efficient TBD-Catalyzed Synthesis of Capsaicin-like Molecules Andrea Defant, Michele Demozzi and

Enzym e-Catalyzed Regioselective Acylation of the Quinic and Shikim ic Acid Derivatives Prof.

Northeasterns Evolution Catalyzed by Data Analytics Kathy Spiegelman Vice President &amp;

Dust from AGBs and the ISM in the Early Universe Dust-catalyzed H 2 Formation Andy Liao, 4 th Year

Ionic liquid [Et 3 NH] [HSO 4 ]-catalyzed Multi component Synthesis of 6-amino-4-(substituted

Open to public submission of BATs (Benchmarkable Which public-key systems Asymmetric Tools).

Bioresource management problem with asymmetric players A.N. Rettieva Institute of Applied

Directed connected operators: Asymmetric hierarchies for image filtering and segmentation

Northeasterns Evolution Catalyzed by Data Analytics Kathy Spiegelman Vice President &