In the investigation of efficient chemical transformations, the carbon-carbon bond-forming reactions play an outstanding role. In this context, organocatalytic processes have achieved considerable attention. 1 Beside their facile reaction course, selectivity, and environmental friendliness, new synthetic strategies are made possible. Particularly, the inversion of the classical reactivity (Umpolung) opens up new synthetic pathways. 2 In nature, the coenzyme thiamine (vitamin B1), a natural thiazolium salt, utilizes a catalytic variant of this concept in biochemical processes as nucleophilic acylations. 3 The catalytically active species is a nucleophilic carbene. 4

Organocatalysis by N-Heterocyclic Carbenes

Asymmetric enamine catalysis.

Small-molecule H-bond donors in asymmetric catalysis.

4.2.8. Reductive Coupling 3109 5. Reaction of Aromatic Compounds 3110 5.1. Electrophilic Substitutions 3110 5.2. Radical Substitution 3111 5.3. Oxidative Coupling 3111 5.4. Photochemical Reactions 3111 6. Reaction of Carbonyl Compounds 3111 6.1. Nucleophilic Additions 3111 6.1.1. Allylation 3111 6.1.2. Propargylation 3120 6.1.3. Benzylation 3121 6.1.4. Arylation/Vinylation 3121 6.1.5. Alkynylation 3121 6.1.6. Alkylation 3121 6.1.7. Reformatsky-Type Reaction 3122 6.1.8. Direct Aldol Reaction 3122 6.1.9. Mukaiyama Aldol Reaction 3124 6.1.10. Hydrogen Cyanide Addition 3125 6.2. Pinacol Coupling 3126 6.3. Wittig Reactions 3126 7. Reaction of R,â-Unsaturated Carbonyl Compounds 3127

Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade Update

Over the past decade, the most significant, conceptual advances in the field of fluorination were enabled most prominently by organo- and transition-metal catalysis. The most challenging transformation remains the formation of the parent C-F bond, primarily as a consequence of the high hydration energy of fluoride, strong metal-fluorine bonds, and highly polarized bonds to fluorine. Most fluorination reactions still lack generality, predictability, and cost-efficiency. Despite all current limitations, modern fluorination methods have made fluorinated molecules more readily available than ever before and have begun to have an impact on research areas that do not require large amounts of material, such as drug discovery and positron emission tomography. This Review gives a brief summary of conventional fluorination reactions, including those reactions that introduce fluorinated functional groups, and focuses on modern developments in the field.

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Introduction of Fluorine and Fluorine-Containing Functional Groups

Organoaluminum-Promoted Rearrangement of Epoxysilanes to α- Silylaldehydes.

N-(Diphenylmethylene)glycine tert-butyl ester



Benzyl bromide



Toluene



Potassium hydroxide



(S)-4,4-Dibutyl-2,6-bis(3,4,5-trifluorophenyl)-4,5-dihydro-3H-dinaphtho[2,1-c:1',2'-e]azepinium bromide



(R)-2-(Benzhydrylidenamino)-3-phenylpropanoic acid tert-butyl ester


Keywords:

Enantioselective alkylation;
N-(diphenylmethylene)glycinate tert-butyl ester;
(R)-2-(benzhydrylidenamino)-3-phenylpropanoic acid tert-butyl ester;
Chiral phase-transfer catalysts;
Glycine derivative

Enantioselective Alkylation of N-(Diphenylmethylene)glycinate tert-Butyl Ester: Synthesis of (R)-2-(Benzhydrylidenamino)-3-Phenylpropanoic Acid tert-Butyl Ester

Methylaluminum Bis(2,6-di-tert-butyl-4-methylphenoxide) as a Protecting Group for Multifunctional Molecules: Synthetic Utility in Selective Carbonyl Reductions.

Asymmetric redox C−C bond formation between α-alkyl-α-diazocarbonyl compounds and aldehydes was developed as a practical and general method for the construction of α-alkyl-β-keto imides having a chiral nonracemic tertiary stereogenic center.

Stereoselective Synthesis of α‐Alkyl‐β‐keto Imides via Asymmetric Redox C—C Bond Formation Between α‐Alkyl‐α‐diazocarbonyl Compounds and Aldehydes.

Phase-transfer alkylation of the benzophenone Schiff base of glycine methyl or ethyl ester ( 2 ) was found to be catalyzed by 3,4,5-F 3 -C 6 H 2 -NAS-Br [ ( S , S )- 1 ] with high efficiency and excellent enantioselectivity. This procedure allows facile derivatization of the resulting alkylation products to other synthetically useful chiral building blocks.

Keiji Maruoka

Papers

Organoaluminum-Promoted Rearrangement of Epoxysilanes to α- Silylaldehydes.

Enantioselective Alkylation of N-(Diphenylmethylene)glycinate tert-Butyl Ester: Synthesis of (R)-2-(Benzhydrylidenamino)-3-Phenylpropanoic Acid tert-Butyl Ester

Methylaluminum Bis(2,6-di-tert-butyl-4-methylphenoxide) as a Protecting Group for Multifunctional Molecules: Synthetic Utility in Selective Carbonyl Reductions.

Stereoselective Synthesis of α‐Alkyl‐β‐keto Imides via Asymmetric Redox C—C Bond Formation Between α‐Alkyl‐α‐diazocarbonyl Compounds and Aldehydes.

Highly Enantioselective Alkylation of Glycine Methyl and Ethyl Ester Derivatives under Phase-Transfer Conditions: Its Synthetic Advantage.