Iron(0)-Mediated Reformatsky Reaction for the Synthesis of β-Hydroxyl Carbonyl Compounds

Liu, Xuan‐Yu; Li, Xiangrui; Zhang, Chen; Chu, Xiangcheng; Rao, Weidong; Loh, Teck‐Peng; Shen, Zhi‐Liang

doi:10.1021/acs.orglett.9b01999

Cited by 17 publications

(4 citation statements)

References 104 publications

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“…Based on the above results and studies reported in the previous reference, a tentative mechanism for the Cu-Catalyzed, Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides was proposed in Fig. 3 [ 52 – 56 ]. Mn, which is severed as a strong reducing agent, reduced the Cu I to Cu 0 in an active form in situ.…”

Section: Introductionmentioning

confidence: 80%

Cu-catalyzed, Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides

et al. 2022

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A simple, practical, and high chemo-selective method for the synthesis of propargyl alcohol and allenyl alcohols via Cu-catalyzed, Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides has been established. When 3-bromo-1-propyne was conducted under the standard condition, the aldehydes were transformed to the corresponding propargylation products completely, while when 1-bromo-2-pentyne was used, allenic alcohol was the only product. Variety of homopropargyl alcohols and allenyl alcohols were obtained in high yields and the reaction is compatible with broad substrate scopes. In addition, the large-scale reaction could also be proceeded smoothly indicating the potential synthetic applications of this transformation. Graphical Abstract

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Section: Introductionmentioning

confidence: 80%

Cu-catalyzed, Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides

et al. 2022

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“…In addition, in contrast to most of the aforementioned relatively expensive metallic catalysts (usually stoichiometric amounts), iron(III) salts, which have been proven to be robust Lewis acids for catalyzing a wide range of organic transformations, [11,12] are more attractive because they are cheaper and less toxic. In continuation of our interest in iron chemistry [13] and in developing efficient methods for the synthesis of fluorine-containing organic molecules, [14] herein we report an efficient iron(III)-catalyzed difluoroalkylation of aryl alkyne with difluoroenol silyl ether in the presence of trimethylsilyl chloride [15] in dichloroethane (DCE), leading to the corresponding products of αalkenyl-α,α-difluoroketones in moderate to good yields (Scheme 1c).…”

Section: Introductionmentioning

confidence: 99%

Iron(III)‐Catalyzed Difluoroalkylation of Aryl Alkynes with Difluoroenol Silyl Ether in the Presence of Trimethylsilyl Chloride

et al. 2022

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The reaction of non‐fluorinated silyl enol ether with alkyne is useful for the synthesis of β,γ‐unsaturated carbonyl compounds. However, most of the existing methods for realizing such organic transformation usually employ stoichiometric amounts of relatively expensive Lewis acids/metallic salts. Herein, an iron(III)‐catalyzed difluoroalkylation of aryl alkynes with difluoroenol silyl ether was developed. The reactions proceeded smoothly in the presence of a catalytic amount of iron(III) chloride, stoichiometric amounts of trimethylsilyl chloride, and 4 Å molecular sieves in dichloroethane (DCE) to afford the corresponding α‐alkenyl‐α,α‐difluoroketones in modest to good yields. Remarkably, among the various metallic salts screened, cheap and less‐toxic iron(III) salt was found to be the most efficient Lewis acid catalyst for the present reaction. In addition, in the absence of iron(III) chloride or trimethylsilyl chloride, either no reaction occurred or considerably reduced reaction performance was observed. Moreover, the use of Brønsted acid to replace iron(III) chloride as reaction catalyst failed to promote the reaction. The reaction could be scaled up and the obtained difluoroalkylated carbonyl compound serves as a versatile building block which could be subjected to late‐stage diversification to be converted into useful organic molecules containing CF2H and CF2CF2 moieties. Deuterated experiments showed that the proton in the generated alkene product should originate from trace amounts of water present in the reaction system.

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“…Since its introduction, the Reformatsky reaction has emerged as one of the most widespread strategies for the formation of new carbon–carbon bonds . To date, various methods based on metal-mediated Reformatsky reactions of α-halo carbonyl compounds with aldehydes or ketones have been widely developed. − Among the reported methods, homogeneous enantioselective Reformatsky-type reactions based on the use of Me 2 Zn have been successfully employed to generate chiral β-hydroxy esters . A breakthrough in the development of Me 2 Zn-mediated catalytic enantioselective Reformatsky reactions with aldehydes or ketones as electrophiles has been made by Cozzi and coauthors.…”

Section: Introductionmentioning

confidence: 99%

Highly Catalytic Enantioselective Reformatsky Reaction with Aldehydes and Ketones Using an Available Prolinol Ligand

et al. 2020

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A highly Me 2 Zn-mediated catalytic enantioselective Reformatsky reaction of aldehydes and ketones with ethyl iodoacetate using a readily available prolinol ligand is reported. This reaction provides an efficient method for the construction of β-hydroxy esters in up to 98% yield and 95% enantiomeric excess (ee) value. A wide range of functional groups are tolerated and the practicality of this protocol is demonstrated by performing the reaction on a gram scale.

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Iron(0)-Mediated Reformatsky Reaction for the Synthesis of β-Hydroxyl Carbonyl Compounds

Cited by 17 publications

References 104 publications

Cu-catalyzed, Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides

Cu-catalyzed, Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides

Iron(III)‐Catalyzed Difluoroalkylation of Aryl Alkynes with Difluoroenol Silyl Ether in the Presence of Trimethylsilyl Chloride

Highly Catalytic Enantioselective Reformatsky Reaction with Aldehydes and Ketones Using an Available Prolinol Ligand

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