Organoborane compounds present a class of versatile synthetic intermediate for myriad organic transformations. The direct addition B–H bond across unsaturated bond—namely, hydroboration—is powerful tool the preparation organoborane derivatives. This review outlines recent advances in catalytic hydroboration compounds, specifically those involving C-X (X = N, O) bonds. We will discuss chemical behavior both transition metal catalysts and main group hydroboration. Emphasis also be placed on...

Hydrophosphination of CO2 with 1,3,2-Diazaphospholene (NHP-H; 1) afforded phosphorus formate (NHP-OCOH; 2) through the formation a bond between electrophilic atom in 1 and oxygen from , along hydride transfer to carbon . Transfer 2 Ph2 SiH2 produced Si(OCHO)2 (3) reaction that could be carried out catalytic manner by using 5 mol % 1. These elementary reactions were applied metal-free N-formylation amine derivatives one pot under ambient conditions.

Abstract The first metal‐free catalytic hydroboration of carbonyl derivatives has been developed in which a amount 1,3,2‐diazaphospholene effectively promotes reaction aliphatic and aromatic aldehydes ketones. mechanism involves the cleavage both PO bond alkoxyphosphine intermediate BH pinacolborane as well formation PH BO bonds. Thus, proceeds through non‐metal σ‐bond metathesis. Kinetic computational studies suggest that metathesis occurred stepwise but nearly concerted manner.

Abstract 1,3,2‐diazaphospholenes catalyze metal‐free transfer hydrogenation of a NN double bond using ammonia–borane under mild reaction conditions, thus allowing access to various hydrazine derivatives. Kinetic and computational studies revealed that the rate‐determining step involves simultaneous breakage BH NH bonds ammonia–borane. The is therefore viewed as concerted type hydrogenolysis.

N-Heterocyclic phosphenium triflates (NHP-OTf) 1 serve as efficient catalysts for the regio- and chemoselective hydroboration of pyridines under ambient condition with good functional group tolerance. Mechanistic studies indicate that a boronium salt, [(Py)2·Bpin]OTf 4, is generated concomitant NHP-H 5 via hydride abstraction from HBpin by in initial reaction step. Hydride reduction activated pyridine 4 affords 1,4-hydroboration product selectively. Thus, species act hydrogen transfer...

Abstract Hydrophosphination of CO 2 with 1,3,2‐Diazaphospholene (NHP‐H; 1 ) afforded phosphorus formate (NHP‐OCOH; through the formation a bond between electrophilic atom in and oxygen from , along hydride transfer to carbon . Transfer Ph SiH produced Si(OCHO) ( 3 reaction that could be carried out catalytic manner by using 5 mol % These elementary reactions were applied metal‐free N‐formylation amine derivatives one pot under ambient conditions.

1,3,2-Diazaphospholene 1 catalyzes the conjugate transfer hydrogenation as well 1,4-hydroboration of α,β-unsaturated esters. The initial step for both processes involves a 1,4-hydrophosphination esters to afford phosphinyl enol ether. Subsequent cleavage P–O bond in ether by ammonia-borane (AB) generates an intermediate which tautomerizes saturated esters, while HBpin via formal σ-bond metathesis affords boryl enolate intermediate. latter could undergo further coupling reaction with nitriles...

Abstract 1,3,2‐diazaphospholenes catalyze metal‐free transfer hydrogenation of a NN double bond using ammonia–borane under mild reaction conditions, thus allowing access to various hydrazine derivatives. Kinetic and computational studies revealed that the rate‐determining step involves simultaneous breakage BH NH bonds ammonia–borane. The is therefore viewed as concerted type hydrogenolysis.

Abstract The first metal‐free catalytic hydroboration of carbonyl derivatives has been developed in which a amount 1,3,2‐diazaphospholene effectively promotes reaction aliphatic and aromatic aldehydes ketones. mechanism involves the cleavage both PO bond alkoxyphosphine intermediate BH pinacolborane as well formation PH BO bonds. Thus, proceeds through non‐metal σ‐bond metathesis. Kinetic computational studies suggest that metathesis occurred stepwise but nearly concerted manner.

The first example of 1,2,4,3-triazaborole-based oxoborane has been synthesized via hydrogen migration upon the coordination AlCl3 to corresponding borinic acid. X-ray diffraction analysis and computational study disclosed partial B[double bond, length as m-dash]O double-bond property.

We have developed bis(N-heterocyclic olefin) derivatives 2 and demonstrated that can be utilized as precursors for the synthesis of isophosphindolylium species 3. X-ray diffraction density functional theory studies indicate aromatic property PC4 five-membered ring in Despite its cationic nature, P center 3b exhibits nucleophilic character thus readily forms a bond with CuCl to afford copper phosphenium complex 4, demonstrating potential utility 3 σ-donor ligand.

The phosphinoimino-2-imidazoline 4 was synthesized by a salt elimination reaction between LiNIPr [NIPr = 1,3-bis(2,6-(diisopropylphenyl)imidazolin-2-ylidenamino)] and 2-chloro-1,3,2-diazaphospholene. DFT study revealed that the HOMO of involves lone pair orbitals on P atom N at exocyclic P–N bond. Compound displays selectivity in coordinating to acids. Thus, bond coordinates hard acid (HCl) which eventually led cleavage bond, while central forms dative with soft Lewis acid, BH3.

Abstract The first metal‐free catalytic hydroboration of carbonyl derivatives is developed in which a amount 1,3,2‐diazaphospholene effectively promotes reaction aliphatic and aromatic aldehydes ketones.

Abstract A novel 1,3,2‐diazaphospholene‐catalyzed N‐formylation of amine derivatives with carbon dioxide in one pot under ambient conditions is described.

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Abstract The reduction of azoarenes (I) with ammonia—borane leads to hydrazines (II), whilst the reaction substrates (III) affords anilines (IV).