The borrowing hydrogen (BH) principle, also called hydrogen auto-transfer, is a powerful approach which combines transfer hydrogenation (avoiding the direct use of molecular hydrogen) with one or more intermediate reactions to synthesize more complex molecules without the need for tedious separation or isolation processes. The strategy which usually relies on three steps, (i) dehydrogenation, (ii) intermediate reaction, and (iii) hydrogenation, is an excellent and well-recognized process from the synthetic, economic, and environmental point of view. In this context, the objective of the present review is to give a global overview on the topic starting from those contributions published prior to the emergence of the BH concept to the most recent and current research under the term of BH catalysis. Two main subareas of the topic (homogeneous and heterogeneous catalysis) have been identified, from which three subheadings based on the source of the electrophile (alkanes, alcohols, and amines) have been consid...

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Advances in One-Pot Synthesis through Borrowing Hydrogen Catalysis

The conservation of our element resources is a fundamental challenge of mankind. The development of alcohol refunctionalization reactions is a possible fossil carbon conservation strategy since alcohols can be obtained from indigestible and abundantly available biomass. The conservation of our rare noble metals, frequently used in key technologies such as catalysis, might be feasible by replacing them with highly abundant metals. The alkylation of amines by alcohols and related C–C coupling reactions are early examples of alcohol refunctionalization reactions. These reactions follow mostly the borrowing hydrogen or hydrogen autotransfer catalysis concept, and many 3d-metal catalysts have been disclosed in recent years. In this review, we summarize the progress made in developing Cu, Ni, Co, Fe, and Mn catalysts for C–N and C–C bond formation reactions with alcohols and amines using the borrowing hydrogen or hydrogen autotransfer concept. We expect that the findings in this field will inspire others to dev...

3d-Metal Catalyzed N- and C-Alkylation Reactions via Borrowing Hydrogen or Hydrogen Autotransfer

Transition-metal-catalyzed C-alkylation of ketones and secondary alcohols, with alcohols, avoids use of organometallic or environmentally unfriendly alkylating agents by means of borrowing hydrogen (BH) or hydrogen autotransfer (HA) activation of the alcohol substrates. Water is formed as the only by-product, thus making the BH process atom-economical and environmentally benign. Diverse homogeneous and heterogeneous transition-metal catalysts, ketones, and alcohols can be used for this transformation, thus rendering the BH process promising for replacing those procedures that use traditional alkylating agents. This Minireview summarizes the advances during the last five years in transition-metal-catalyzed BH α-alkylation of ketones, and β-alkylation of secondary alcohols with alcohols. A discussion on the application of the BH strategy for C-C bond formation is included.

C-Alkylation of Ketones and Related Compounds by Alcohols: Transition-Metal-Catalyzed Dehydrogenation.

This paper summarizes recent advances in α-alkylation reactions based on hydrogen borrowing methodologies using alcohol as an alkylating agent. This review provides a summary of recent progress toward the α-alkylation of carbonyl substrates, as well as relatively unactivated substrates bearing fewer acidic α-hydrogens, such as acetonitriles, acetamides, esters, methylpyrimidines, and methylquinolines. A summary of recent improvements in α-methylation strategies based on hydrogen borrowing methodologies has also been provided. Particular emphasis has been placed on highly practical and green chemistry approaches involving modified catalytic systems, including metal-supported heterogeneous catalysts and nanoparticle-based catalysts, as well as reactions conducted in the absence of a transition-metal catalyst. A review of recent achievements in methylation strategies using methanol as a methyl source, and their application to the α-methylation of ketones using transition-metal catalyzed hydrogen borrowing me...

Recent Advances in α-Alkylation Reactions using Alcohols with Hydrogen Borrowing Methodologies

Over the past few years, iridium complexes have been widely used in the direct functionalization of unactivated bonds. In the presence of iridium catalysts, inactive C–H and N–H bonds have been transformed into C–C and N–C bonds in dehydrative alkylation using alcohols, allylation using allyl carbonates, and alkylation using alkenes. Enantioselective variants of some reactions have also been reported.

Recent Advances in Iridium-Catalyzed Alkylation of C–H and N–H Bonds

Synthesis of ω‐Hydroxy Carboxylic Acids and α,ω‐Dimethyl Ketones Using α,ω‐Diols as Alkylating Agents.

Synthesis of omega-hydroxy carboxylic acids and alpha,omega-dimethyl diketones was successfully achieved by using alpha,omega-diols as alkylating agents under the influence of an iridium catalyst. For example, the alkylation of butyl cyanoacetate with 1,13-tridecanediol in the presence of [IrCl(cod)](2) or [IrCl(coe)(2)](2) gave rise to butyl 2-cyano-15-hydroxypentadecanoate in good yield which is easily converted to cyclopentadecanolide (CPDL). In addition, the alkylation of acetone with 1,10-decanediol in the presence of [IrCl(cod)](2) and KOH resulted in an important muscone precursor, 2,15-hexadecanedione (HDDO), in good yield.

Synthesis of omega-hydroxy carboxylic acids and alpha,omega-dimethyl ketones using alpha,omega-diols as alkylating agents.

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Synthesis of ω‐Hydroxy Carboxylic Acids and α,ω‐Dimethyl Ketones Using α,ω‐Diols as Alkylating Agents.

Synthesis of omega-hydroxy carboxylic acids and alpha,omega-dimethyl ketones using alpha,omega-diols as alkylating agents.