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Natural Products as Inspiration for Reaction Development: Catalytic Enantioselective Decarboxylative Reactions of Prochiral Enolate Equivalents

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Inventing Reactions

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 44))

Abstract

This account describes the circumstances leading to our group’s innovations in the area of decarboxylative asymmetric allylic alkylation reactions and the initial discovery of palladium phosphinooxazoline complexes as efficient enantioselective catalysts. This chapter also chronicles the growth of the methodology to include several substrate classes, the expansion of the project into several other reaction manifolds, and the use of these reactions in natural product synthesis. Finally, important contributions from other research groups involving related methods or products similar to the α-quaternary products that are the focus of our studies, as well as future directions for asymmetric alkylation reactions, are discussed.

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Notes

  1. 1.

    This law, which is known to many in Caltech’s Chemistry and Chemical Engineering Division, is based on Prof. John E. Bercaw’s observation that for a surprisingly large number of reactions, a brief initial optimization often provides results that cannot be surpassed by an exhaustive follow-on optimization effort.

Abbreviations

4ÅMS:

4 Ångström molecular sieves

ACN:

Acetonitrile

AIBN:

2,2′-Azobis(2-methylpropionitrile)

BSA:

O,N-bistrimethylsilyl acetamide

Dba:

Dibenzylideneacetone

DME:

Dimethoxyethane

DMSO:

Dimethylsulfoxide

Dppf:

1,1′-Bis(diphenylphosphino)ferrocene

Dr:

Diastereomeric ratio

Ee:

Enantiomeric excess

KHMDS:

Potassium bis(trimethylsilyl)amide

LDA:

Lithium diisopropylamide

LHMDS:

Lithium bis(trimethylsilyl)amide

PCC:

Pyridinium chlorochromate

PHOX:

Phosphinooxazoline

Piv:

Pivaloyl

Pmdba:

Bis(p-methoxybenzylidene)acetone

TBAT:

Tetrabutylammonium difluorotriphenylsilicate

TBS:

t-Butyldimethylsilyl

TEA:

Triethylamine

THF:

Tetrahydrofuran

TMS:

Trimethylsilyl

QUINAP:

1-(2-Diphenylphosphino-1-naphthyl)isoquinoline

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Author information

Authors and Affiliations

  1. Division of Chemistry and Chemical Engineering, The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, 91125, USA

    Douglas C. Behenna & Brian M. Stoltz

Authors
  1. Douglas C. Behenna
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  2. Brian M. Stoltz
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Correspondence to Brian M. Stoltz .

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Editors and Affiliations

  1. , FB Chemie - Organische Chemie, TU Kaiserslautern, Erwin-Schrödinger-Str. 54, Kaiserslautern, 67663, Germany

    Lukas J. Gooßen

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Behenna, D.C., Stoltz, B.M. (2012). Natural Products as Inspiration for Reaction Development: Catalytic Enantioselective Decarboxylative Reactions of Prochiral Enolate Equivalents. In: Gooßen, L. (eds) Inventing Reactions. Topics in Organometallic Chemistry, vol 44. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3418_2012_49

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