Morita Baylis Hillman Carbonates Research Articles

ChemInform Abstract: Highly Enantioselective Regiodivergent Allylic Alkylations of MBH Carbonates with Phthalides.

AbstractPhthalides are used for the first time in allylic alkylation reactions with Morita—Baylis—Hillman carbonates for the preparation of chiral 3,3‐disubstituted phthalides.

Organocatalytic asymmetric allylic amination of Morita–Baylis–Hillman carbonates of isatins

The investigation of a Lewis base catalyzed asymmetric allylic amination of Morita–Baylis–Hillman carbonates derived from isatins afforded an electrophilic pathway to access multifunctional oxindoles bearing a C3-quaternary stereocenter, provided with good to excellent enantioselectivity (up to 94% ee) and in high yields (up to 97%).

Direct Asymmetric Allylic Alkenylation of N-Itaconimides with Morita–Baylis–Hillman Carbonates

The asymmetric allylic alkenylation of Morita-Baylis-Hillman (MBH) carbonates with N-itaconimides as nucleophiles has been developed using a commercially available Cinchona alkaloid catalyst. A variety of multifunctional chiral α-methylene-β-maleimide esters were attained in moderate to excellent yields (up to 99%) and good to excellent enantioselectivities (up to 91% ee). The origin of the regio- and stereoselectivity was verified by DFT methods. Calculated geometries and relative energies of various transition states strongly support the observed regio- and enantioselectivity.

Asymmetric Allylic Alkylation of Isatin-Derived Morita–Baylis–Hillman Carbonates with Nitroalkanes

A stereoselective allylic alkylation of isatin-derived Morita-Baylis-Hillman (MBH) carbonates with nitroalkanes has been developed. In the presence of 10 mol % β-isocupreidine (β-ICD), 3,3'-disubstituted oxindoles were prepared with moderate diastereoselectivities and excellent enantioselectivities.

Enantioselective synthesis of spirocyclic cyclopentenes: asymmetric [3+2] annulation of 2-arylideneindane-1,3-diones with MBH carbonates derivatives catalyzed by multifunctional thiourea–phosphines

The [3+2] annulation reactions of 2-arylideneindane-1,3-diones with Morita–Baylis–Hillman (MBH) carbonates proceeded smoothly in the presence of multifunctional thiourea–phosphines to produce the corresponding quaternary carbon centered spirocyclic cyclopentenes in moderate yields, with high diastereoselectivities and enantioselectivities under mild conditions. The plausible reaction has been also discussed on the basis of previous literature.

ChemInform Abstract: Diastereo‐ and Enantioselective [3 + 2] Cycloaddition Reaction of Morita—Baylis—Hillman Carbonates of Isatins with N‐Phenylmaleimide Catalyzed by Me‐DuPhos.

AbstractThe reaction allows an efficient access to optically active spirocyclic oxindoles of biological interest.

Chiral multifunctional thiourea-phosphine catalyzed asymmetric [3 + 2] annulation of Morita–Baylis–Hillman carbonates with maleimides

We have developed a multifunctional thiourea-phosphine catalyzed asymmetric [3 + 2] annulation of Morita–Baylis–Hillman (MBH) carbonates with maleimides, which can efficiently construct functionalized cyclopentenes bearing three contiguous stereocenters in moderate to excellent yields and excellent diastereo- and enantioselectivities. A plausible mechanism has been also proposed on the basis of control experiments and previous literature.

ChemInform Abstract: Enantioselective Synthesis of Highly Functionalized Trifluoromethyl‐Bearing Cyclopentenes: Asymmetric [3 + 2] Annulation of Morita—Baylis—Hillman Carbonates with Trifluoroethylidenemalonates Catalyzed by Multifunctional Thiourea‐Phosphines.

On the basis of the design and synthesis of multifunctional thiourea-phosphines, a catalytic method for the asymmetric [3+2] annulation of Morita–Baylis–Hillman carbonates with trifluoroethylidenemalonates has been developed, affording highly functionalized trifluoromethyl-bearing cyclopentenes in excellent yields, high diastereoselectivities and enantioselectivities under mild conditions.

ChemInform Abstract: Asymmetric Assembly of 2‐Oxindole and α‐Angelica Lactone Units to Construct Vicinal Quaternary Chiral Centers.

AbstractAn oxygen‐bridged quinidine derivative is successfully used as a chiral catalyst for the allylic alkylation of Morita—Baylis—Hillman carbonates (I) with lactones (II).

Cinchona Alkaloid Catalyzed Regio‐ and Enantioselective Allylic Amination of Morita–Baylis–Hillman Carbonates with Isatins

AbstractAn efficient enantioselective allylic amination of Morita–Baylis–Hillman (MBH) carbonates derived from methyl acrylate and aromatic aldehydes with isatins has been realized in the presence of commercially available cinchona alkaloids. The allylic amination products were obtained in moderate‐to‐good yields (46–74 %) with moderate‐to‐good enantioselectivities (up to 89 % ee) under mild conditions. The synthetic utility of the amination products has been well demonstrated by the facile synthesis of methyl (3R,4R)‐10‐oxo‐4‐phenyl‐2,3,4,10‐tetrahydropyrimido[1,2‐a]indole‐3‐carboxylate.

Organocatalytic enantioselective substitution of MBH carbonates by 2-fluoromalonates

The enantioselective fluoromalonate addition to Morita–Baylis–Hillman carbonates is presented. The reaction is simply catalyzed by β-isocupreidine affording the final fluorinated products in good yields and enantioselectivities.

ChemInform Abstract: Preparation of Chiral Multifunctional Thiourea—Phosphanes and Synthesis of Chiral Allylic Phosphites and Phosphane Oxides Through Asymmetric Allylic Substitution Reactions of Morita—Baylis—Hillman Carbonates.

AbstractThe reactions apply chiral multifunctional thiourea‐phosphane catalyst (TPB) to afford allylic phosphites and phosphane oxides in high yields and enantioselectivities.

ChemInform Abstract: Lewis Base Assisted Broensted Base Catalysis: Direct Asymmetric Allylic Alkylation of Indenes.

AbstractThe first allylic alkylation of indene derivatives with Morita—Baylis—Hillman carbonates (I) is catalyzed by (DHQD)2‐AQN to give the desired products with high enantioselectivities but only moderate yields.

ChemInform Abstract: Organocatalytic Asymmetric C—S Bond Formation: Synthesis of α‐Methylene‐β‐mercapto Esters with Simple Alkyl Thiols.

AbstractA highly efficient asymmetric reaction of Morita—Baylis—Hillman carbonates (I) and (IV) with alkyl mercaptans (II) is achieved in the presence of MgSO4 and (DHQD)2‐PHAL as organocatalyst.

Diastereo- and Enantioselective [3 + 2] Cycloaddition Reaction of Morita–Baylis–Hillman Carbonates of Isatins with N-Phenylmaleimide Catalyzed by Me-DuPhos

A Me-DuPhos-catalyzed efficient asymmetric [3 + 2] cycloaddition reaction between Morita-Baylis-Hillman carbonates of isatins and N-phenylmaleimide has been developed. This reaction constructs three chiral centers in one step to afford spirocyclopentaneoxindoles in good yields (up to 84%) with excellent diastereo- and enantioselectivies (up to 99% ee).

ChemInform Abstract: Organocatalytic Enantioselective Amination of Morita—Baylis—Hillman Carbonates with Masked Ammonia: A Facile Method for the Synthesis of Unprotected α‐Methylene‐β‐amino Esters.

ChemInform Abstract: Organocatalytic Enantioselective Amination of Morita—Baylis—Hillman Carbonates with Masked Ammonia: A Facile Method for the Synthesis of Unprotected α‐Methylene‐β‐amino Esters.

ChemInform Abstract: Organocatalytic Enantioselective Methodologies Using Morita—Baylis—Hillman Carbonates and Acetates

AbstractReview: 40 refs.

Enantioselective Synthesis of Highly Functionalized Trifluoromethyl‐Bearing Cyclopentenes: Asymmetric [3+2] Annulation of Morita–Baylis–Hillman Carbonates with Trifluoroethylidenemalonates Catalyzed by Multifunctional Thiourea‐Phosphines

AbstractOn the basis of the design and synthesis of multifunctional thiourea‐phosphines, a catalytic method for the asymmetric [3+2] annulation of Morita–Baylis–Hillman carbonates with trifluoroethylidenemalonates has been developed, affording highly functionalized trifluoromethyl‐bearing cyclopentenes in excellent yields, high diastereoselectivities and enantioselectivities under mild conditions.

ChemInform Abstract: Highly Enantioselective and Regioselective Substitution of Morita—Baylis—Hillman Carbonates with Nitroalkanes.

AbstractThe use of MBH carbonates bearing an alkyl substituent is not possible in the process.

ChemInform Abstract: Asymmetric Allylic Monofluoromethylation and Methylation of Morita—Baylis—Hillman Carbonates with FBSM and BSM by Cooperative Cinchona Alkaloid/FeCl2 Catalysis.

AbstractAsymmetric allylic monofluoromethylation of Morita—Baylis—Hillman products with FBSM (II) proceeds with high yields and enantioselectivities in the presence of (DHQD)2AQN organocatalyst.