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The Allylic Trihaloacetimidate Rearrangement

Larry E. Overman

University of California, Irvine, Irvine, California

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Nancy E. Carpenter

University of Minnesota, Morris, Minnesota

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First published: 15 December 2005
Cited by: 31

Abstract

Sigmatropic rearrangements of allylic systems have found wide application in organic synthesis, with carbon‐carbon bond forming rearrangements such as the Cope and Claisen rearrangements being particularly well known. The sigmatropic rearrangement of allylic imidates offers a valuable entry into the preparation of protected allylic amines. Conversion of an imidate to the amide is essentially irreversible, with the transformation of the imidate to the amide being exothermic by about 15 kcal/mol. Since the discovery of the thermal allylic imidate rearrangement in 1937, a number of systems have been investigated for the practical preparation of allylic amines by this route. However, it was the discovery and development of the rearrangement of allylic trichloroacetamidates that demonstrated the utility of this synthetic method.

This chapter is limited to the discussion of allylic trichloro‐ and trifluoracetamidate rearrangements. The [3,3]‐sigmatropic rearrangement of trichloracetamidates (now called the Overman rearrangement) or trifluoroacetimidates can be carried out either thermally or with Hg(II) or Pd(II) catalysis, The scope of this rearrangement is such that primary, secondary, and tertiary allylic amides are readily accessible, thus providing a wide entry into nitrogen‐containing products such as amino sugars, nucleotides, peptides, etc. The Overman rearrangement has found extensive application in the total synthesis of natural products. The recent development of the use of chiral Pd(II) catalysts bodes well for amine synthesis.

Number of times cited: 31

  • , The Allyl Cyanate/Isocyanate Rearrangement: An Efficient Tool for the Stereocontrolled Formation of Allylic C–N Bonds, European Journal of Organic Chemistry, 2017, 10, (1295-1307), (2017).
  • , Spiropiperidine Sultam and Lactam Templates: Diastereoselective Overman Rearrangement and Metathesis followed by NH Arylation, The Journal of Organic Chemistry, 82, 23, (12246), (2017).
  • , Rearrangement of Benzylic Trichloroacetimidates to Benzylic Trichloroacetamides, The Journal of Organic Chemistry, 82, 7, (3982), (2017).
  • , Computational Studies on an Aminomethylation Precursor: (Xantphos)Pd(CH2NBn2)+, Organometallics, 35, 10, (1582), (2016).
  • , Synthesis of Chiral, Enantiopure Allylic Amines by the Julia Olefination of α-Amino Esters, Molecules, 21, 12, (805), (2016).
  • , Cutting-Edge and Time-Honored Strategies for Stereoselective Construction of C–N Bonds in Total Synthesis, Chemical Reviews, 10.1021/acs.chemrev.5b00712, 116, 7, (4441-4557), (2016).
  • , Enantioselective Total Synthesis of (+)‐Neostenine, Chemistry – A European Journal, 22, 10, (3300-3303), (2016).
  • , Sulfinyl-Mediated Stereoselective Overman Rearrangements and Diels–Alder Cycloadditions, The Journal of Organic Chemistry, 10.1021/acs.joc.6b00365, 81, 10, (4081-4097), (2016).
  • , [2,3]‐Rearrangements of Ammonium Zwitterions, Molecular Rearrangements in Organic Synthesis, (459-496), (2015).
  • , Competitive Pseudopericyclic [3,3]- and [3,5]-Sigmatropic Rearrangements of Trichloroacetimidates, The Journal of Organic Chemistry, 80, 23, (11734), (2015).
  • , Ferrier Carbocyclization Reaction, Molecular Rearrangements in Organic Synthesis, (363-400), (2015).
  • , Computational Studies on Sigmatropic Rearrangements via π‐Activation by Palladium and Gold Catalysts, Understanding Organometallic Reaction Mechanisms and Catalysis, (93-120), (2014).
  • , Diastereoselective synthesis of highly substituted polycyclic scaffolds via a one-pot four-step tandem catalytic process, Tetrahedron, 10.1016/j.tet.2014.06.020, 70, 40, (7133-7141), (2014).
  • , Phosphonium salt induced stereoselective allylic rearrangement during chlorination of α-hydroxyallylphosphinates, Tetrahedron Letters, 10.1016/j.tetlet.2014.08.118, 55, 42, (5742-5744), (2014).
  • , Transition‐Metal‐Catalyzed Allylic Substitutions of Trichloroacetimidates, European Journal of Organic Chemistry, 2014, 23, (4925-4948), (2014).
  • , Synthesis of Natural Products Containing Cyclohexane Units Utilizing the Ferrier Carbocyclization Reaction, The Chemical Record, 14, 4, (592-605), (2014).
  • , BRØNSTED ACID–CATALYZED CASCADE REACTIONS, Catalytic Cascade Reactions, (53-122), (2013).
  • , Multicomponent Domino Process: Rational Designand Serendipity, Domino Reactions, (579-610), (2013).
  • , Enantioselective Passerini Reaction, Asymmetric Synthesis II, (95-101), (2013).
  • , Enantioselective Rhodium‐Catalyzed Synthesis of Branched Allylic Amines by Intermolecular Hydroamination of Terminal Allenes, Angewandte Chemie, 124, 43, (11034-11037), (2012).
  • , Enantioselective Rhodium‐Catalyzed Synthesis of Branched Allylic Amines by Intermolecular Hydroamination of Terminal Allenes, Angewandte Chemie International Edition, 51, 43, (10876-10879), (2012).
  • , A Highly Enantioselective Overman Rearrangement through Asymmetric Counteranion‐Directed Palladium Catalysis, Angewandte Chemie International Edition, 50, 41, (9752-9755), (2011).
  • , Hoch enantioselektive Overman‐Umlagerung durch asymmetrische Gegenanionen‐vermittelte Palladium‐Katalyse, Angewandte Chemie, 123, 41, (9926-9929), (2011).
  • , Total Synthesis of (−)‐Salinosporamide A, Chemistry – An Asian Journal, 6, 1, (209-219), (2010).
  • , Asymmetric Carbon–Heteroatom Bond‐Forming Reactions, Catalytic Asymmetric Synthesis, (227-267), (2010).
  • , Allylic Imidate Rearrangements Catalyzed by Planar Chiral Palladacycles, Chemistry – An Asian Journal, 5, 8, (1726-1740), (2010).
  • , The Allylic Trihaloacetimidate Rearrangement, ChemInform, 37, 46, (2006).
  • , 1‐(2,2‐Dimethoxyethyl)‐2‐isocyanobenzene, Encyclopedia of Reagents for Organic Synthesis, (2010).
  • , 1‐Isocyano‐2‐nitrobenzene, Encyclopedia of Reagents for Organic Synthesis, (2010).
  • , 1‐Isocyanocyclohex‐1‐ene, Encyclopedia of Reagents for Organic Synthesis, (2010).
  • , Catalytic Isohypsic‐Redox Sequences for the Rapid Generation of Csp3‐Containing Heterocycles, Chemistry – A European Journal, , (2018).