Chiral phosphine lewis bases catalyzed asymmetric aza-Baylis-Hillman reaction of N-sulfonated imines with activated olefins.
26 Feb 2005-Journal of the American Chemical Society (American Chemical Society)-Vol. 127, Iss: 11, pp 3790-3800
TL;DR: An effective bifunctional Lewis base and Bronsted acid phosphine Lewis base system has been disclosed in this catalytic, asymmetric aza-Baylis-Hillman reaction and the mechanistic insight has been investigated by 31P and 1H NMR spectroscopic measurements.
Abstract: In the aza-Baylis-Hillman reaction of N-sulfonated imines (N-arylmethylidene-4-methylbenzenesulfonamides and others) with methyl vinyl ketone, ethyl vinyl ketone, and acrolein, we found that, in the presence of a catalytic amount of chiral phosphine Lewis base such as (R)-2'-diphenylphosphanyl-[1,1']binaphthalenyl-2-ol LB1 (10 mol %) and molecular sieve 4A, the corresponding aza-Baylis-Hillman adducts could be obtained in good yields with good to high ee (70-95% ee) at low temperature (approximately -30 to -20 degrees C) or at room temperature in THF, respectively. In CH2Cl2 upon heating at 40 degrees C, the aza-Baylis-Hillman reaction of N-sulfonated imines with phenyl acrylate or naphthyl acrylate gave the adducts in good to high yields (60-97%) with moderate ee (52-77%). The mechanistic insight has been investigated by 31P and 1H NMR spectroscopic measurements. The key enolate intermediate, which has been stabilized by intramolecular hydrogen bonding, has been observed by 31P and 1H NMR spectroscopy. An effective bifunctional Lewis base and Bronsted acid phosphine Lewis base system has been disclosed in this catalytic, asymmetric aza-Baylis-Hillman reaction.
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TL;DR: It has become increasingly apparent that the behavior of Lewis bases as agents for promoting chemical reactions is not merely as an electronic complement of the cognate Lewis acids: in fact Lewis bases are capable of enhancing both the electrophilic and nucleophilic character of molecules to which they are bound.
Abstract: The legacy of Gilbert Newton Lewis (1875-1946) pervades the lexicon of chemical bonding and reactivity. The power of his concept of donor-acceptor bonding is evident in the eponymous foundations of electron-pair acceptors (Lewis acids) and donors (Lewis bases). Lewis recognized that acids are not restricted to those substances that contain hydrogen (Bronsted acids), and helped overthrow the "modern cult of the proton". His discovery ushered in the use of Lewis acids as reagents and catalysts for organic reactions. However, in recent years, the recognition that Lewis bases can also serve in this capacity has grown enormously. Most importantly, it has become increasingly apparent that the behavior of Lewis bases as agents for promoting chemical reactions is not merely as an electronic complement of the cognate Lewis acids: in fact Lewis bases are capable of enhancing both the electrophilic and nucleophilic character of molecules to which they are bound. This diversity of behavior leads to a remarkable versatility for the catalysis of reactions by Lewis bases.
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TL;DR: Acyclic activated alkenes/ alkynes and Asymmetric Baylis-Hillman Reaction: Earlier Developments 5495.
Abstract: 2. Essential Components: Earlier Developments 5449 2.1. Activated alkenes/alkynes 5450 2.1.1. Acyclic activated alkenes/ alkynes 5450 2.1.2. Cyclic activated alkenes 5451 2.2. Electrophiles 5451 2.3. Catalysts 5452 3. Essential Components: Recent Developments 5452 3.1. Activated Alkenes/Alkynes 5452 3.2. Electrophiles 5460 3.3. Catalysts 5477 4. Asymmetric Baylis-Hillman Reaction: Earlier Developments 5495
752 citations
TL;DR: This Review documents recent advances in asymmetric catalysis, with special emphasis on the most innovative asymmetric processes and the development of novel, efficient types of ferrocene ligands.
Abstract: Despite the impressive progress achieved in asymmetric catalysis during the last decade, an increasing number of new catalysts, ligands, and applications are reported every year to satisfy the need to embrace a wider range of reactions and to improve the efficiency of existing processes. Because of their availability, unique stereochemical aspects, and wide variety of coordination modes and possibilities for the fine-tuning of the steric and electronic properties, ferrocene-based ligands constitute one of the most versatile ligand architectures in the current scenario of asymmetric catalysis. Over the last few years ferrocene catalysts have been successfully applied in an amazing variety of enantioselective processes. This Review documents these recent advances, with special emphasis on the most innovative asymmetric processes and the development of novel, efficient types of ferrocene ligands.
651 citations
TL;DR: 1.5.1.
Abstract: 2.3.3. Fluorinated Imines 7 2.3.4. Arylimino Acetates 8 2.3.5. In Situ Generated Iminium Ions 8 2.4. -Substituted Michael Acceptors 8 2.5. Formation of Unexpected Products 10 2.5.1. Reaction with Cyclic Enones 11 2.5.2. Reaction with Vinyl Ketones 11 2.5.3. Reaction with Acrolein 12 2.5.4. Reaction with Activated Allenes and Alkynes 12 2.5.5. Reaction of Salicyl N-Tosylimines 12 3. Stereoselective Synthesis 13 3.1. Use of Chiral Aldehydes 13 3.2. Use of Chiral Bases 13 3.3. Use of Chiral Phosphines 16 3.4. Use of a Chiral Sulfide 18 3.5. Use of an Organocatalyst Derived from BINOL 18 3.6. Use of a Chiral Ligand Derived from Thiourea 18 3.7. Use of Chiral Ionic Liquids 18 4. Alternative Access Pathways to -Aminocarbonyl Compounds 18
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TL;DR: Easily accessible [(salen)(iPrO)Al] exerts excellent molecular-weight and stereochemical control in lactide polymerization either in solution or in the absence of solvent.
Abstract: Easily accessible [(salen)(iPrO)Al] exerts excellent molecular-weight and stereochemical control in lactide polymerization either in solution or in the absence of solvent. The R,R initiator shows a marked preference for L-lactide over D-lactide. Stereoblock copolylactides with high melting points can be prepared directly from d,l-lactides by using a racemic initiator.
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TL;DR: The Brønsted-acid-catalyzed reaction is the first example of a highly enantioselective asymmetric MBH reaction of cyclohexenone with aldehydes.
Abstract: Chiral BINOL-derived Bronsted acids catalyze the enantioselective asymmetric Morita−Baylis−Hillman (MBH) reaction of cyclohexenone with aldehydes The asymmetric MBH reaction requires 2−20 mol % of the chiral Bronsted acid 2e or 2f and triethylphosphine as the nucleophilic promoter The reaction products are obtained in good yields (39−88%) and high enantioselectivities (67−96% ee) The Bronsted-acid-catalyzed reaction is the first example of a highly enantioselective asymmetric MBH reaction of cyclohexenone with aldehydes
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TL;DR: A mechanistic proposal governed by hydrogen bonding is presented to give (S)-enriched N-protected-alpha-methylene-beta-amino acid esters, which shows the opposite enantioselectivity to the corresponding aldehydes.
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