← Back to Search
Addressing The Configuration Stability Of Lithiated Secondary Benzylic Carbamates For The Development Of A Noncryogenic Stereospecific Boronate Rearrangement.
K. Fandrick, N. Patel, J. Mulder, J. Gao, M. Konrad, Elizabeth Archer, F. Buono, A. Duran, R. Schmid, J. Daeubler, Daniel R Fandrick, Shengli Ma, N. Grinberg, Heewon Lee, C. Busacca, J. Song, N. Yee, C. Senanayake
Published 2014 · Medicine, Chemistry
Download PDFAnalyze on Scholarcy
A practical noncryogenic process for the Aggarwal stereospecific boronate rearrangement with chiral secondary benzylic carbamates has been developed. The use of LDA instead of sec-BuLi combined with an in situ trapping of the unstable lithiated carbamate was critical to success. Furthermore, this new process increased the substrate scope to include the versatile aryl iodide and bromide substrates. The methodology was applied to a diverse array of substrates and was demonstrated on multikilogram scale.
This paper references
Asymmetric synthesis of active pharmaceutical ingredients.
V. Farina (2006)
Enantiodivergent conversion of chiral secondary alcohols into tertiary alcohols
Jake L. Stymiest (2008)
Enantioselective construction of quaternary stereogenic centers from tertiary boronic esters: methodology and applications.
Ravindra P. Sonawane (2011)
Thorough Examination of a Wittig−Horner Reaction Using Reaction Calorimetry (RC-1), LabMax, and ReactIR
Michael Grabarnick (2003)
Improved method for the conversion of pinacolboronic esters into trifluoroborate salts: facile synthesis of chiral secondary and tertiary trifluoroborates
Viktor Bagutski (2009)
Alkoxyalkyl)boronic Ester Intermediates for Asymmetric Synthesis
D. Matteson (1996)
Chiral Lithium‐1‐oxyalkanides by Asymmetric Deprotonation; Enantioselective Synthesis of 2‐Hydroxyalkanoic Acids and Secondary Alkanols
D. Hoppe (1990)
Another possibility exists where internal protonation of the deprotonated carbamate occurs from the diisopropylamine during the deuterium quench ; see :
K. R. Fandrick (1988)
Concise synthesis of a selective α1-adrenoceptor antagonist
T. Connolly (2006)
Transition Metal Catalysis in the Pharmaceutical Industry
C. Busacca (2012)
Boronic Esters in Stereodirected Synthesis
D. Matteson (1989)
Enantioselective Synthesis with Lithium/(−)‐Sparteine Carbanion Pairs
D. Hoppe (1997)
Alkylation of amino acids without loss of the optical activity: preparation of .alpha.-substituted proline derivatives. A case of self-reproduction of chirality
D. Seebach (1983)
The mechanism of the lithium-halogen interchange reaction: a review of the literature
W. Bailey (1988)
Highly enantioselective synthesis of tertiary boronic esters and their stereospecific conversion to other functional groups and quaternary stereocentres.
H. K. Scott (2011)
Full chirality transfer in the conversion of secondary alcohols into tertiary boronic esters and alcohols using lithiation-borylation reactions.
Viktor Bagutski (2010)
Asymmetric deprotonation of N-boc piperidine: react IR monitoring and mechanistic aspects.
Darren Stead (2010)
Eds.; RSC Publishing
M. T. Williams (2011)
Homologation and alkylation of boronic esters and boranes by 1,2-metallate rearrangement of boronate complexes.
S. Thomas (2009)
.alpha.-Halo boronic esters: intermediates for stereodirected synthesis
D. Matteson (1989)
This paper is referenced by
On the design of complex drug candidate syntheses in the pharmaceutical industry
Martin D. Eastgate (2017)
Development of an Efficient Synthesis of (2-Aminopyrimidin-5-yl) Boronic Acid
N. Patel (2016)
Transition-metal-free synthesis of 1,1-diboronate esters with a fully substituted benzylic center via diborylation of lithiated carbamates.
Haonan Zhao (2017)
Early Development Scale-Up of a Structurally-Challenging 5-Lipoxygenase Activating Protein (FLAP) Inhibitor
Jason Mulder (2017)
Development of αGlcN(1↔1)αMan-Based Lipid A Mimetics as a Novel Class of Potent Toll-like Receptor 4 Agonists
Florian Adanitsch (2014)
Generation, structure and reactivity of tertiary organolithium reagents.
M. Perry (2015)
Development of an Efficient Asymmetric Synthesis of the Chiral Quaternary 5-Lipoxygenase Activating Protein Inhibitor
Keith R Fandrick (2016)
6. Synthesis of Organoboronic Acids, Organoboronates, and Related Compounds
Robert A Stockland (2016)
Lithiation-borylation methodology and its application in synthesis.
Daniele Leonori (2014)
Full chirality transfer in the synthesis of hindered tertiary boronic esters under in situ lithiation-borylation conditions.
D. J. Blair (2016)
Addressing the Configuration Stability of Lithiated Secondary Benzylic Carbamates for the Development of a Noncryogenic Stereospecific Boronate Rearrangement.
Keith R. Fandrick (2015)
Preparation of 1-Substituted Tetrahydro-β-carbolines by Lithiation-Substitution.
Edward J. Cochrane (2015)
1,2‐Metallate Rearrangement of Boron Derivatives
J. M. Bateman (2019)
Development of an asymmetric synthesis of a chiral quaternary FLAP inhibitor.
K. Fandrick (2015)