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Related Concept Videos

Regioselectivity and Stereochemistry of Hydroboration02:36

Regioselectivity and Stereochemistry of Hydroboration

A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Hydroboration-Oxidation of Alkenes03:08

Hydroboration-Oxidation of Alkenes

In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation02:47

Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation

Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Preparation of Alcohols via Addition Reactions02:15

Preparation of Alcohols via Addition Reactions

Overview
The acid-catalyzed addition of water to the double bond of alkenes is a large-scale industrial method used to synthesize low-molecular-weight alcohols. An acidic atmosphere is required to allow the hydrogen in the water molecule to act as an electrophile and attack the double bond in an alkene. The addition of a proton to the double bond creates a carbocation intermediate. The proton preferentially bonds to the less substituted end of the double bond to create a more stable carbocation...
Radical Anti-Markovnikov Addition to Alkenes: Mechanism01:17

Radical Anti-Markovnikov Addition to Alkenes: Mechanism

The reaction of hydrogen bromide with alkenes in the presence of hydroperoxides or peroxides proceeds via anti-Markovnikov addition. The radical chain reaction comprises initiation, propagation, and termination steps.
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy radical...
Regioselectivity of Electrophilic Additions-Peroxide Effect02:35

Regioselectivity of Electrophilic Additions-Peroxide Effect

In the presence of organic peroxides, the addition of hydrogen bromide to an alkene yields the isomer that is not predicted by Markovnikov’s rule. For example, the addition of hydrogen bromide to 2-methylpropene in the presence of peroxides gives 1-bromo-2-methylpropane. This addition reaction proceeds via a free radical mechanism, which reverses the regioselectivity. The free radical reaction mechanism involves three stages: initiation, propagation, and termination.

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Synthesis of a Borylated Ibuprofen Derivative Through Suzuki Cross-Coupling and Alkene Boracarboxylation Reactions
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Synthesis of a Borylated Ibuprofen Derivative Through Suzuki Cross-Coupling and Alkene Boracarboxylation Reactions

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Oxygen-directed intramolecular hydroboration.

Robert-André F Rarig1, Matthew Scheideman, Edwin Vedejs

  • 1Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, USA.

Journal of the American Chemical Society
|June 25, 2008
PubMed
Summary
This summary is machine-generated.

This study introduces a metal-free intramolecular hydroboration method for homoallylic alcohols. The process achieves high regioselectivity for 1,3-dioxy-substituted products, enhanced by C5 branching.

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Area of Science:

  • Organic Chemistry
  • Synthetic Chemistry
  • Catalysis

Background:

  • Intramolecular hydroboration is a key synthetic transformation.
  • Developing metal-free catalytic systems is a significant goal in organic synthesis.
  • Directing group strategies are crucial for controlling regioselectivity.

Purpose of the Study:

  • To report a novel metal-free homoallylic oxygen-directed intramolecular hydroboration.
  • To achieve high regioselectivity in the hydroboration of homoallylic alcohols.
  • To investigate the effect of substrate branching on regioselectivity.

Main Methods:

  • Utilized a metal-free system employing dimethyl sulfide borane (Me2S.BH3) and triflic acid (TfOH).
  • Employed oxygen-directed intramolecular hydroboration of homoallylic alcohols.
  • Performed standard oxidative workup to yield the final products.

Main Results:

  • Achieved high regioselectivities ranging from 20:1 to 82:1.
  • Demonstrated a strong preference for the formation of 1,3-dioxy-substituted products.
  • Observed that branching at the C5 position of the substrate significantly improves regioselectivity.

Conclusions:

  • The developed method offers an efficient and selective route to valuable oxygenated organic compounds.
  • This metal-free approach provides a greener alternative to traditional hydroboration methods.
  • Substrate structural modifications, like C5 branching, can be strategically employed to enhance reaction outcomes.