Transition Metal-Mediated Cycloaddition Reactions

Abstract

Contents 1. Introduction 49 2. Three-Membered Ring Formation 50 2.1. [2 + 1] Cycloadditions Using Stoichiometric Amounts of Zinc Carbenoids (Simmons−Smith Type) 50 2.2. [2 + 1] Cycloadditions with Stoichiometric Amounts of Samarium Carbenoids 52 2.3. [2 + 1] Cycloadditions with Transition Metal-Stabilized Alkyl Carbenes of Cu, Pd, Ni, Co, and Rh 52 2.4. Cyclopropanations with Metal Carbenes Derived from R-Diazocarbonyl Compounds 54 2.5. [2 + 1] Cycloadditions with Vinylcarbenes 54 2.6. [2 + 1] Cycloadditions with Palladium Complexes of Oxatrimethylenemethane 56 2.7. Transition Metal-Catalyzed Aziridinations 57 3. Four-Membered Ring Formation 58 3.1. [2 2π + 2 2π ] Cycloadditions of Strained Alkenes with Electron-Deficient Olefins 58 3.2. [2 2π + 2 2π ] Cycloadditions of Strained Alkenes with Acetylenes 59 3.3. Intramolecular [2 2π + 2 2π ] Cycloadditions 60 4. Five-Membered Ring Formation 60 4.1. [3 2σ + 2 2π ] Cycloadditions with Metallacyclobutanes 60 4.2. [3 2σ + 2 2π ] Cycloadditions with Pd−Trimethylenemethane Complexes 61 4.3. Intramolecular [3 2σ + 2 2π ] Cycloadditions with Pd−TMM Complexes 62 4.4. [3 2σ + 2 2π ] Cycloadditions with Methylenecyclopropane 64 4.5. Intramolecular [3 2σ + 2 2π ] Cycloadditions with Methylenecyclopropanes 66 4.6. [3 4π + 2 2π ] Cycloadditions with Metal Carbenoids 67 4.7. [4 4π + 1 2π ] Cycloadditions 69 5. Six-Membered Ring Formation 69 5.1. [2 2π + 2 2π + 2 2π ] Cycloadditions 69 5.2. Acetylene [2 2π + 2 2π + 2 2π ] Cyclotrimerization Reactions 70 5.3. Acetylene−Olefin [2 2π + 2 2π + 2 2π ] Cyclotrimerizations 71 5.4. Hetero [2 2π + 2 2π + 2 2π ] Cyclotrimerizations 72 5.5. Homo-Diels−Alder [2 2π + 2 2π + 2 2π ] Cycloadditions 72 5.6. Bis-Homo-Diels−Alder [2 2π + 2 2π + 2 2π ] Cycloadditions 74 5.7. [3 2π + 3 2σ ] Cycloadditions 74 5.8. [4 4π + 2 2π ] Cycloadditions 75 6. Seven-Membered Ring Formation 78 6.1. [4 4π + 3 2σ ] Cycloadditions 78 6.2. [5 2π+2σ + 2 2π ] Cycloadditions 79 7. Eight-Membered Ring Formation 79 7.1. [2 2π + 2 2π + 2 2π + 2 2π ] Cycloadditions 80 7.2. [4 4π + 2 2π + 2 2π ] Cycloadditions 80 7.3. [4 4π + 4 4π ] Cycloadditions 81 7.4. [6 6π + 2 2π ] Cycloadditions 83 8. Ten-Membered Ring Formation 85 9. Conclusion and Remarks 87 49

Tandem diastereo- and enantioselective preparation of aryl and alkyl cyclopropyl carbinols with three adjacent stereocenters using perhydrobenzoxazines and diethylzinc

“…1,2 Additionally, due to the three-membered ring strain, these compounds can undergo an assortment of synthetically useful ring-opening reactions. 3,4 For these reasons, novel and more efficient methodologies for the preparation of enantiopure cyclopropanes are continuously emerging.…”

“…3,4 For these reasons, novel and more efficient methodologies for the preparation of enantiopure cyclopropanes are continuously emerging. [1][2][3]5 To date, the different synthetic strategies can be generally classified into three main groups. 1j In first place, the transition metal-catalyzed decomposition of diazoalkanes has been probably one of the most studied approaches for the cyclopropanation of olefins, and very important advances in terms of stereoselectivity have been achieved in this area employing diazocompounds and chiral auxiliaries as well as chiral catalysts.…”

“…1j In first place, the transition metal-catalyzed decomposition of diazoalkanes has been probably one of the most studied approaches for the cyclopropanation of olefins, and very important advances in terms of stereoselectivity have been achieved in this area employing diazocompounds and chiral auxiliaries as well as chiral catalysts. 1,6 More recently, a promising strategy has emerged from the organocatalysis, which allowed the synthesis of enantioenriched cyclopropanes, usually via a Michael-initiated ring closure. 1,7 Another approach to the stereoselective synthesis of cyclopropanes concerns the halomethylmetal-mediated cyclopropanation reactions, which is commonly known as Simmons-Smith reaction.…”

“…1,6 More recently, a promising strategy has emerged from the organocatalysis, which allowed the synthesis of enantioenriched cyclopropanes, usually via a Michael-initiated ring closure. 1,7 Another approach to the stereoselective synthesis of cyclopropanes concerns the halomethylmetal-mediated cyclopropanation reactions, which is commonly known as Simmons-Smith reaction. 1,8 Although the first report by Emschwiller dates from 1929, 9 in which diiodomethane was reacted with zinc to give iodomethylzinc species, more than 30 years were necessary for the introduction of the cyclopropanation of alkenes with diiodomethane in the presence of activated zinc by Simmons and Smith.…”

“…1,7 Another approach to the stereoselective synthesis of cyclopropanes concerns the halomethylmetal-mediated cyclopropanation reactions, which is commonly known as Simmons-Smith reaction. 1,8 Although the first report by Emschwiller dates from 1929, 9 in which diiodomethane was reacted with zinc to give iodomethylzinc species, more than 30 years were necessary for the introduction of the cyclopropanation of alkenes with diiodomethane in the presence of activated zinc by Simmons and Smith. 10 Since then, different alternative procedures for the preparation of a variety of metal carbenoid species have been developed, and one of the most popular methods is the alkyl exchange of diethylzinc with diiodomethane.…”