, Prepared using N-benzyl allylamine as nucleophile and purified using a cyclohexane/ethyl acetate mixture (70/30, R f 0.54) as eluent. The product was isolated as a colorless oil (46 mg) in 55% yield. 1 H NMR (400 MHz, CDCl, vol.828, 1028.
51 Prepared using benzyl alcohol as nucleophile and purified using a cyclohexane/ethyl acetate mixture (80/20, R f 0.50) as eluent. The product was isolated as a colorless oil (33 mg) in 45% yield. 1 H NMR (300 MHz, CDCl 3 ) ? 7.37-7.32 (m, 5H), vol.7, p.carbamate ,
, 30 (Trichloromethyl)benzene (1.75 mmol) and 0.59 mL of H 2 17 O were placed in a microwave vessel and sealed. The resulting mixture was irradiated with microwaves at 150 W, p.130
, Once the mixture was cooled down to room temperature, the solid formed was filtered and washed with hexane. The desired pure compound was obtained as a white solid, p.93
, 400 MHz, Acetone-d 6 ): ? 8.07-8.02 (m, 2H), 7.66-7.60 (m, 1H), 7.51 (dd, J = 8.4, 7.1 Hz, 2H). 17 O NMR (68 MHz, vol.6, p.245
, 31 To a solution of
, 60 mmol) was dissolved in THF (20 mL). A solution of LiAlH 4 in THF (1.48 mL, 2.5 M) was slowly added to the resulting mixture at 0 °C and the reaction was allowed to stir at room temperature until total consumption of starting material, toluene (10 mL) ethyl diazoacetate was added dropwise (3.24 mmol) and the resulting mixture was warmed up to 80 ºC and stirred for 12h, vol.7, p.10
, The organic layers were dried over MgSO 4 , filtered and concentrated in vacuo. The final product was purified by flash column chromatography on silica gel using a hexane/ethyl acetate mixture (60/40
One of us (S.H.) thanks La region Bretagne and VillaPharma Research for a research fellowship. M.A. thanks the Eusko Jaurlaritza-Gobierno Vasco for her PhD fellowship. I. R. and F. P. C. thank the SGI/IZOSGIker UPV/EHU and the DIPC for generous allocation of computational and analytical resources. REFERENCES (1) Some selected reviews on ,
, Sigmatropic Rearrangements. Synthesis, vol.3, pp.961-1008, 2003.
, Sigmatropic Rearrangements: Recent Applications in the Total Synthesis of Natural Products
Sigmatropic Rearrangement of Allylic Trichloroacetimidates. 1,3 Transposition of Alcohol and Amine Functions, Organic reactions, vol.38, pp.597-599, 1974. ,
, , vol.66, pp.1-107, 2005.
Recent Advances in Overman Rearrangement: Synthesis of Natural Products and Valuable Compounds, For recent reviews, see: (a), vol.15, pp.2672-2710, 2009. ,
A New Thermal Rearrangement of Allylic Phenylurethans, For the pioneer work, see: (a), vol.33, pp.1111-1116, 1968. ,
, Decarboxylative Cyclization of Allylic Cyclic Carbamates: Applications to the Total Synthesis of
, J. Org. Chem, vol.56, pp.4341-4343, 1991.
A Facile Highly Regio-and Stereoselective Preparation of N-Tosyl Allylic Amines from Allyl Alcohols and Tosyl Isocyanate via Palladium ,
, Org. Lett, vol.2, pp.2357-2360, 2000.
, Iridium(I)-Catalyzed Regio-and Enantioselective Decarboxylative Allylic Amidation of Substituted Allyl Benzyl Imidodicarbonates, (I)-Catalyzed Highly Regio-and Stereoselective Decarboxylative Amination of Allylic N-Tosylcarbamates via Base-Induced, vol.129, pp.774-775, 2007.
Rearrangement in Water, Org. Lett, vol.12, pp.1068-1071, 2010. ,
Asymmetric Cascade Reaction to Allylic Sulfonamides from Allylic Alcohols by Palladium(II)/Base-Catalyzed Rearrangement of Allylic Carbamates, Angew. Chem. Int. Ed, vol.53, pp.7634-7638, 2014. ,
Dual Palladium(II)/Tertiary Amine Catalysis for Asymmetric Regioselective Rearrangements of ,
Synthesis of, Chem. Eur. J, vol.22, pp.5767-5777, 2016. ,
Esters Utilizing Palladium-Catalyzed Rearrangement of Allylic Carbamates for Direct Application to Formal [3+2] Cycloaddition, Org. Lett, vol.19, pp.1682-1685, 2017. ,
Alkyl Cyanates. XIV. Isomerization of Allylic Cyanates and Allylic Thionoderivatives, Acta Chem. Scand, vol.24, pp.1512-1526, 1970. ,
, a) Ichikawa, I. Evolution, Development and Personal Experience in Studies of The Allyl Cyanate-to
The Allyl Cyanate/Isocyanate Rearrangement : An Efficient Tool for the Stereocontrolled Formation of Allylic C-N Bonds, Eur. J. Org. Chem, pp.1295-1307, 2007. ,
URL : https://hal.archives-ouvertes.fr/hal-01515165
Regioselective Allylamine Construction, Halichondria Sp ,
, J. Chem. Soc. Perkin Trans. 1, pp.2429-2432, 1993.
, Tricyclic Core of FR901483 Featuring a Rh-Catalyzed [2+2+2] Cycloaddition, Synthesis, vol.45, pp.719-728, 2013.
Sigmatropic Rearrangements of Fluorinated Allyl (Thio)cyanates-A Tool for the Synthesis of Fluorinated (Thio)ureas, Chimia, vol.3, pp.436-441, 2014. ,
Sigmatropic Rearrangement of Boronated Allylcyanates: A New Route to ?-Aminoboronate Derivatives and Trisubstituted Tetrahydrofurans, Sigmatropic Rearrangement/Allylboration/Cyclization Sequence: Enantioenriched Seven-Membered-Ring Carbamates and Ring Contraction to Pyrrolidines, vol.3, pp.2712-2715, 2013. ,
URL : https://hal.archives-ouvertes.fr/hal-00861083
, , vol.55, pp.1025-1029, 2016.
, Mild Formation of Functionalized Disiloxanes, J. Org. Chem, vol.81, pp.4633-4644, 2016.
Asymmetric Synthesis of trans-4,5-disubstituted ?butyrolactones involving a key allylboration step. First access to (-)-nicotlactone B and (-)-galbacin ,
URL : https://hal.archives-ouvertes.fr/hal-01744288
For the first observation of this rearrangement in the gas phase, see: (a) Lewis, E. S.; Hill, J. T, vol.16, issue.10, pp.1672-1678, 2018. ,
Rearrangement of Esters in the Gas Phase. II. Substituent Effects on the Rate of Isomerization of Allyllic Esters, J; Am. Chem ,
Rearrangement of Esters in the Gas Phase. IV. Fate of an Oxygen Tracer in the Rearrangement of Crotyl Trifluoroacetate, J. Am. Chem. Soc, vol.90, pp.1167-1171, 1968. ,
, For a recent computational study of the sigmatropic rearrangement of allyl esters, see: (a)
Sigmatropic Rearrangements of Esters Are Pseudopericyclic ,
Sigmatropic Rearrangements of Acetoxycyclohexadienones: A non-ionic Mechanism for Acyl Migration, J. Am. Chem. Soc, vol.38, issue.13, pp.1-40, 1976. ,
Synthesis of Highly Functionalized AB Taxane Ring System: Formation of the Eight-Membered Ring by an Efficient 8-exo-tet Alkylation of an ?-Sulfonyl Anion, and references cited therein. (b), vol.23, pp.85-86, 1984. ,
Complementary Reactions of Allylic Carbamates Using Palladium (II): Formation of Oxazolidinones or Allylic Amides from a Common Precursor, Chem. Eur. J, vol.21, pp.19119-19127, 2009. ,
For some recent examples of allyl carbamates, see: (a) ,
The Regioselective Aminohydroxylation of Allylic Carbamates, Chem. Commun, pp.2078-2079, 2001. ,
Palladium-Catalyzed Ring-Forming Aminoacetoxylation of ,
Phosphine Oxide-Sc(Otf) 3 Catalyzed Highly Regio-and Enantioselective Bromoaminocyclization of (E)-Cinnamyl Tosylcarbamates. An Approach to a Class of Synthetically Versatile Functionalized Molecules, Tetrahedron, vol.127, pp.896-899, 2005. ,
Organic Carbamates in Drug Design and Medicinal Chemistry, J. Med. Chem, vol.58, pp.2895-2940, 2015. ,
, This kind of allyl carbamates are generally synthesized from the reaction of primary allyl alcohols with isocyanates
Pentamethylcyclopentadienyl Ruthenium: an Efficient Catalyst for the Redox Isomerization of Functionalized Allylic Alcohols into Carbonyl Compounds, The (E)-3-(4-methoxyphenyl)prop-2-en-1-ol was prepared from anisaldehyde according to the following publication, vol.64, pp.11745-11750, 2008. ,
URL : https://hal.archives-ouvertes.fr/hal-00356814
For some recent synthetic applications of dienyl carbamates, see: (a) Donohoe, T ,
Tethered Aminohydroxylation: Dramatic Improvements to the Process ,
Rhodium-Catalyzed Regioand Stereoselective Oxyamination of Dienes via Tandem Aziridination/Ring-Opening of Dienyl Carbamates, Org. Lett, vol.9, pp.1725-1728, 2007. ,
, Chem. Commun, vol.50, pp.7344-7347, 2014.
Enantioselective Synthesis of Aminodiols by Sequential Rhodium-Catalysed Oxyamination/Kinetic Resolution: Expanding the Substrate Scope of Amidine-Based Catalysis, Chem. Eur. J, vol.24, pp.4635-4642, 2018. ,
The Synthesis of 5-Amino-dihydrobenzo[b]oxepines and 5-Amino-dihydrobenzo[b]azepines via Ichikawa Rearrangement and Ring-Closing Metathesis, J. Org. Chem, vol.81, pp.9046-9071, 2016. ,
Ti-Catalyzed Reactions of Hindered Isocyanates with Alcohols, J. Org. Chem, vol.70, pp.6118-6121, 2005. ,
, No formation of 11 and 12 at room temperature in the absence of Et 3 N and DMAP. Alkyl carbamate 12 can also be prepared from 1a and isopropyl isocyanate using CuCl as catalyst
, Copper(I) Chloride Catalyzed Addition of Alcohols to Alkyl Isocyanates. A Mild and Expedient Method for
, Alkyl Carbamate Formation, Synthesis, pp.131-132, 1989.
, To avoid a slight formation of rearranged products during the purification, a prior deactivation of silica gel with triethylamine has been necessary
One-Pot Synthesis of Optically Active Allyl Esters via Lipase-Vanadium Combo Catalysis, Org. Lett, vol.12, pp.4900-4903, 2010. ,
From (S)-20, the carbamoylation/rearrangement sequence is complete after 1 h at room temperature using tosyl isocyanate. However, the enantiomeric excess of this rearranged product could not be determined due to its instability during HPLC analysis, Competitive Pseudopericyclic, issue.26 ,
, Sigmatropic Rearrangements of Trichloroacetimidates, J. Org. Chem, vol.80, pp.11734-11743, 2015.
CASSCF Calculations Reveal Competitive Chair (Pericyclic) and Boat (Pseudopericyclic) Transition States for the [3,3] Sigmatropic Rearrangement of Allyl Esters, J. Org. Chem, vol.83, pp.1717-1726, 2018. ,
A Three-Component Enantioselective Cyclization Reaction Catalyzed by an Unnatural Amino Acid Derivative, Angew. Chem. Int. Ed, vol.8, issue.30, pp.781-853, 1969. ,
Loss of Isotope Labeling in the Conversion of [ 18 O 2 ]Benzoic Acid into [ 18 O]benzoyl Chloride with Oxalyl Chloride, Angew. Chem. Int. Ed, vol.57, pp.303-305, 2003. ,
Situ Generation of Nitrilium from Nitrile Ylide and the Subsequent Mumm Rearrangement: Copper-Catalyzed Synthesis of Unsymmetrical Diacylglycine Esters, Org. Biomol. Chem, vol.14, pp.10723-10732, 2016. ,
Koppel, I. Effect of Charged and Ortho Substituents on 17 O NMR Chemical Shifts of Substituted Phenyl Tosylates in DMSO, J. Phys. Org. Chem, pp.3870-3883, 2018. ,
Analyzing Reaction Rates with the Distortion/Interaction-Activation Strain Model, Angew. Chem. Int. Ed, vol.56, pp.10070-10086, 2017. ,
A Survey of Hammett Substituent Constants and Resonance and Field Parameters, Chem. Rev, vol.91, pp.165-195, 1991. ,
A Correlation of Reaction Rates, J. Am. Chem. Soc, vol.77, issue.35, pp.334-338, 1955. ,
Chemical and Electrochemical Electron-Transfer Theory, Annu. Rev. Phys. Chem, vol.15, pp.155-196, 1964. ,
Transition State Distortion Energies Correlate with Activation Energies of 1,4Dihydrogenations and Diels-Alder Cycloadditions of Aromatic Molecules, J. Am. Chem. Soc, vol.131, pp.4084-4089, 2009. ,
Distortion/Interaction Energy Control of 1,3-Dipolar Cycloaddition Reactivity, J. Am. Chem. Soc, vol.129, pp.10646-10647, 2007. ,
Organoselenium-Catalyzed, Hydroxy-Controlled Regioand Stereoselective Amination of Terminal Alkenes: Efficient Synthesis of 3-Amino Allylic Alcohols, Org. Lett, vol.17, pp.1834-1837, 2015. ,
,
Synthesis of Allylic Alcohols: Boronic Acid as a Hydroxide Source, Chem. Eur. J, vol.14, pp.5630-5637, 2008. ,
Ruthenium-Catalyzed Tandem-Isomerization/Asymmetric Transfer Hydrogenation of Allylic Alcohols, Chem. Eur. J, vol.20, pp.16102-16106, 2014. ,
Regiocontrol and Stereoselectivity in Tungsten-Bipyridine Catalysed Allylic Alkylation, Tetrahedron, vol.51, pp.8863-8874, 1995. ,
Synthesis of Enantiomerically Pure Lignin Dimer Models for Catalytic Selectivity Studies, J. Org. Chem, vol.80, pp.1771-1780, 2015. ,
Highly Selective 1,3-Isomerization of Allylic Alcohols via Ruthenium Oxo Catalysis, J. Am. Chem. Soc, vol.127, pp.2842-2843, 2005. ,
Highly Diastereo-and Enantio-selective Epoxidation of Secondary Allylic Alcohols Catalyzed by Styrene Monooxygenase, Chem. Commun, vol.47, pp.2610-2612, 2011. ,
Versatile Stereoselective Synthesis of endo,exoFurofuranones: Application to the Enantioselective Synthesis of Furofuran Lignans, J. Org. Chem, vol.69, pp.122-129, 2004. ,
Enantioselective Iridium-Catalyzed Allylic Amination of Racemic Allylic Alcohols, Angew. Chem. Int. Ed, vol.51, pp.3470-3473, 2012. ,
Metal-Free Synthesis of Aryl Ethers in Water, Org. Lett, vol.15, pp.6070-6073, 2013. ,
Reductive Aldol Coupling of Divinyl Ketones via Rhodium-Catalyzed Hydrogenation: syn-Diastereoselective Construction of ?-Hydroxyenones, Org. Lett, vol.8, pp.5657-5660, 2006. ,
Nickel-Catalyzed Cross-Couplings of Allylic Pivalates and Arylboroxines, Org. Lett, vol.16, pp.3596-3599, 2014. ,
, Sulfonyl Azides as Precursors in Ligand-Free Palladium
, Catalyzed Synthesis of Sulfonyl Carbamates and Sulfonyl Ureas and Synthesis of Sulfonamides, J. Org. Chem, vol.81, pp.2681-2691, 2016.
Asymmetric Synthesis of N-Protected Amino Acids by the Addition of Organolithium Carboxyl Synthons to ROPHy/SOPHy-Derived Aldoximes and Ketoximes ,
, Org. Biomol. Chem, vol.2, pp.265-276, 2004.
Organocatalysts Fold To Generate an Active Site Pocket for the Mannich Reaction, ACS Catal, vol.7, pp.3284-3294, 2017. ,
Lewis-Acid Catalyzed Formation of Dihydropyrans, Tetrahedron, vol.67, pp.9870-9884, 2011. ,
Gaussian 09, Revision D.01: Frisch ,
,
,
,
,
,
,
Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density, J. Chem. Phys, vol.98, issue.55, pp.785-789, 1988. ,
A Consistent and Accurate ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu, J. Chem. Phys, vol.132, issue.57, pp.154104-154104, 2010. ,
The OPLS [Optimized Potentials for Liquid Simulations] Potential Functions for Proteins, Energy Minimizations for Crystals of Cyclic Peptides and Crambin, J. Am. Chem. Soc, vol.25, issue.58, pp.1657-1666, 1986. ,
,
OPLS3: A Force Field Providing Broad Coverage of Drug-like Small Molecules and Proteins, J. Chem. Theory Comput, vol.12, pp.281-296, 2016. ,
First Evaluation of Geometries and Properties of Excited Molecules in Solution: A Tamm-Doncoff Model with Application to 4-Dimethylaminobenzonitrile, J. Phys, issue.60, 2018. ,
Quantum Mechanical Continuum Solvatation Models, Chem. Rev, vol.104, pp.2999-3094, 2000. ,
, Natural Hybrid Orbitals. J. Am. Chem. Soc, vol.102, issue.61, pp.7211-7218, 1980.
Natural Population Analysis, J. Chem. Phys, vol.83, pp.735-746, 1985. ,
Intermolecular Interactions from a Natural Bond Orbital, Donor-Acceptor Viewpoint, J. Chem. Phys, vol.83, pp.899-926, 1985. ,