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This work describes a transition metal-free methodology involving an efficient and controlled reduction of isocyanates to only formamide derivatives using pinacolborane (HBpin) as the hydrogenating agent and a bis(phosphino)carbazole ligand stabilized magnesium methyl complex (1) as the catalyst. A large number of substrates undergo selective hydroboration and give exclusively N-boryl formamides. [ABSTRACT FROM AUTHOR]

In contrast to the recent reports on catalytic hydroboration of amides to amines with pinacolborane (HBpin), a simple catalyst-free and solvent-free method for the hydroboration of a variety of amides has been realized. To get the mechanistic insights, DFT calculations have been performed. [ABSTRACT FROM AUTHOR]

A selective and efficient route for the deoxygenative reduction of primary to tertiary amides to corresponding amines has been achieved with pinacolborane (HBpin) using simple and readily accessible 2,6-di-tert-butyl phenolate lithium·THF (1a) as a catalyst. Both experimental and DFT studies provide mechanistic insight. [ABSTRACT FROM AUTHOR]

The hydroboration of alkenes and alkynes using easily accessible lithium compounds [2,6-di-tert-butyl phenolatelithium (1a) and 1,1′ dilithioferrocene (1b)] has been achieved with good yields, high functional group tolerance and excellent chemoselectivity. Deuterium-labeling experiments confirm the cis-addition of pinacolborane. The methodology has been further extended to myrcene, which undergoes selective 4,3-hydroboration. DFT calculations provide insights into the mechanism. [ABSTRACT FROM AUTHOR]

Simple and readily accessible lithium compounds such as 2,6-di-tert-butyl phenolate lithium (1a), 1,1′ dilithioferrocene (1b) and nacnac lithium (1c) are found to be efficient single site catalysts for hydroboration of a range of aldehydes and ketones with HBpin at room temperature. The efficacy of 1a–1c as catalysts is extended to the cyanosilylation of aldehydes and ketones with Me3SiCN. [ABSTRACT FROM AUTHOR]

The transition metal free catalytic hydroboration of aldehydes and ketones is very limited and has not been reported with a well-defined silicon(iv) compound. Therefore, we chose to evaluate the previously reported silicon(iv) hydride [PhC(NtBu)2SiHCl2], (1) as a single component catalyst and found that it catalyzes the reductive hydroboration of a range of aldehydes with pinacolborane (HBpin) under ambient conditions. In addition, compound 1 can catalyze imine hydroboration. DFT calculation was carried out to understand the mechanism. [ABSTRACT FROM AUTHOR]

A new mechanism has been proposed for the hydroboration of aldehydes by germylene and stannylene complexes, with the aid of the hydroborating agent, pinacolborane (HBpin). This new mechanism is demonstrated with computational studies with density functional theory (DFT), not only for existing systems, but also for newly designed germylene and stannylene systems. [Display omitted] The chemistry of low valent main group compounds has grown as an alternative to the chemistry of less abundant and less green transition metal complexes. It has been found that low valent compounds such as carbenes, silylenes, stannylenes and germylenes are efficient for activating small molecules and for catalysis. However, the reaction mechanism and the factors that affect the rate of reaction are not completely understood. In this computational investigation with density functional theory (DFT), we investigate and demonstrate the efficiency of a new mechanism for the hydroboration of aldehydes by germylenes and stannylenes, in the presence of the common hydroborating agent, pinacolborane, HBpin. This mechanism involves an HBpin molecule as an additional catalyst that cooperates with the germylene or stannylene catalyst to efficiently carry out the hydroboration. This mechanism is first demonstrated to work for experimentally reported systems, and then shown to be efficient for newly proposed germylene and stannylene systems. These new systems are α-Borylamido-germylene ((2,6- i Pr 2 C 6 H 3 NBCy 2) 2 Ge(II)) and α-Borylamido-stannylene((2,6- i Pr 2 C 6 H 3 NBCy 2) 2 Sn(II)). These new insights will help researchers look into low valent germylene and stannylene chemistry from a new perspective. [ABSTRACT FROM AUTHOR]

(a) The catalytic application of organolithium compounds is very limited due to their high reactivity and aggregation phenomena. However, the paradigm started to shift recently, when the groups of Okuda (J. Am. Chem. Soc. 2016, 138, 10790) and Mulvey (Chem. Eur. J., 2017, 23, 16853) reported the use of organolithium compounds for the hydroboration of aldehydes and ketones. Nonetheless, the catalytic use of organolithium compounds for reduction of more challenging and synthetically useful substrates such as carbodimides, esters etc. is deemed desirable. (b) Very recently, we have shown the use of organolithium compounds for the hydroboration of aldehydes and ketones (Chem. Commun. 2018, 54, 6843) as well as alkenes and alkynes (Chem. Commun. 2019, 55, 11711). Building upon our previous works, we demonstrate here catalytic hydroboration of ester to alcohol and carbodiimide to imine. (c) Prior to this work, there are few main-group catalysts reported for the hydroboration of carbodiimdies (See Chart 1 in the manuscript), but no well-defined group 1 complex as a single site catalyst has been used. The same is true for ester hydroboration. This is the first report of the catalytic hydroboration of esters and carbodiimides using single site catalyst based on a s -block element. (d) A thorough DFT studies were carried out to understand the mechanism of carbodiimide hydroboration. Selective and efficient hydroboration of esters and carbodiimides to alcohols and amines by two well-defined and readily accessible lithium complexes, 2,6-di-tert-butyl phenolate lithium (1a) and 1,1'-dilithioferrocene (1b) are described. A range of aliphatic, aromatic, and cyclic esters with various functional groups were selectively converted into the corresponding boronate esters. Similarly, the single hydroboration of carbodiimides with aliphatic and aromatic substituents on the nitrogen atoms was studied. A possible mechanistic pathway of the hydroboration of carbodiimides with HBpin has been proposed using NMR studies and DFT calculations. These reactions are convenient alternatives to stoichiometric hydride reduction or hydrogenation. The employing of lithium complexes is also significant, because of the need to find cheap and green alternatives to noble metal complexes. [Display omitted] We have demonstrated the use of simple and readily available lithium compounds, 2,6-di-tert-butyl phenolate lithium (1a) and 1,1'-dilithioferrocene (1b) as single site catalysts for hydroboration of diverse esters and carbodiimides in high yields and excellent functional group tolerance. DFT studies have been performed to understand the mechanism of carbodiimide hydroboration. [ABSTRACT FROM AUTHOR]