Essential Reagents for Organic Synthesis

Philip L. Fuchs, André B. Charette, Tomislav Rovis, Jeffrey W. Bode

• Publisher: Wiley
• Year: 2016
• Print ISBN:
  9781119278306
• eBook ISBN:
  9781119279877
• Edition: 1
• Topic: Physical Sciences
• Subtopic: Physical & Theoretical Chemistry

From Boron Trifluoride to Zinc, the 52 most widely used reagents in organic synthesis are described in this unique desktop reference for every organic chemist. The list of reagents contains classics such as N-Bromosuccinimide (NBS) and Trifluoromethanesulfonic Acid side by side with recently developed ones like Pinacolborane and Tetra-n-propylammonium Perruthenate (TPAP).

For each reagent, a concise article provides a brief description of all important reactions for which the reagent is being used, including yields and reaction conditions, an overview of the physical properties of the reagent, its storage conditions, safe handling, laboratory synthesis and purification methods. Advantages and disadvantages of the reagent compared to alternative synthesis methods are also discussed.

Reagents have been hand-picked from among the 5000 reagents contained in EROS, the Encyclopedia of Reagents for Organic Synthesis. Every organic chemist should be familiar with these key reagents that can make almost every reaction work.

9-Borabicyclo[3.3.1]nonane Dimer¹

[70658-61-6] C₁₆H₃₀B₂ (MW 244.03)

InChI = 1/2C8H15B/c2*1-3-7-5-2-6-8(4-1)9-7/h2*7-9H,1-6H2/t2*7-,8+

InChIKey = FPEQNDQUWPJCKZ-MOGCCKQLBC

(highly selective, stable hydroborating agent;^1,3 anti-Markovnikov hydration of alkenes and alkynes;^1d effective ligation for alkyl-, aryl-, allyl-, allenyl-, alkenyl- and alkynylboranes;^1a,4,5 forms stable dialkylboryl derivatives, borinate esters, and haloboranes;^1f organoboranes from hydroboration and organometallic reagents;^1,5 precursor to boracycles;^1,11 can selectively reduce conjugated enones to allylic alcohols;^1a,30 organoborane derivatives for α-alkylation and arylation of α-halo ketones, nitriles, and esters;^1b vinylation and alkynylation of carbonyl compounds;^1a,46 conjugate addition to enones;^1a,47 homologation; asymmetric reduction;^1,8 Diels–Alder reactions;^1a,18,50 enolboranes for crossed aldol condensations;^1a,20,52 Suzuki–Miyaura coupling^1a,54–57)

1. Alternate Name: 9-BBN-H.
2. Physical Data: mp 153–155 °C (sealed capillary); bp 195 °C/12 mmHg.^1,3
3. Solubility: sparingly sol cyclohexane, dimethoxyethane, diglyme, dioxane (<0.1 M at 25 °C); sol THF, ether, hexane, benzene, toluene, CCl₄, CHCl₃, CH₂Cl₂, SMe₂ (ca. 0.2–0.6 M at 25 °C); reacts with alcohols, acetals, aldehydes, and ketones.^1,3
4. Form Supplied in: colorless, stable crystalline solid; 0.5 M solution in THF or hexanes.
5. Analysis of Reagent Purity: the melting point of 9-BBN-H dimer is very sensitive to trace amounts of impurities. Recrystallization from dimethoxyethane is recommended for samples melting below 146 °C. The dimer exhibits a single ¹¹B NMR (C₆D₆) resonance at δ 28 ppm and ¹³C NMR signals at 20.2 (br), 24.3 (t), and 33.6 (t) ppm.^1,3
6. Handling, Storage, and Precaution: the crystalline 9-BBN-H dimer can be handled in the atmosphere for brief periods without significant decomposition. However, the reagent should be stored under an inert atmosphere, preferably below 0 °C. Under these conditions the reagent is indefinitely stable. In solution, 9-BBN is more susceptible both to hydrolysis and oxidation, and contact with the open atmosphere should be rigorously avoided. Many 9-BBN derivatives are pyrophoric and/or susceptible to hydrolysis so that individuals planning to use 9-BBN-H dimer should thoroughly familiarize themselves with the special techniques required for the safe handling of such reagents prior to their use.^1b The reagent should be used in a well-ventilated hood.

Original Commentary

John A. Soderquist

University of Puerto Rico, Rio Piedras, Puerto Rico

Organoboranes from 9-BBN-H

First identified by Köster,² 9-BBN-H dimer is prepare...

Table of contents

• Cover
• e-EROS Editorial Board
• Title Page
• Copyright
• Preface
• Short Note on InChIs and InChIKeys
• General Abbreviations
• Bis(dibenzylideneacetone)palladium(0)
• 9-Borabicyclo[3.3.1]nonane Dimer
• Boron Trifluoride Etherate
• N-Bromosuccinimide
• n-Butyllithium
• N,N'-Carbonyl Diimidazole
• Cerium (IV) Ammonium Nitrate
• m-Chloroperbenzoic Acid
• N-Chlorosuccinimide
• Chlorotrimethylsilane
• Chlorotris(triphenylphosphine)-rhodium(I)
• (Diacetoxyiodo)benzene
• Diazomethane
• 2,3-Dichloro-5,6-dicyano-1,4-benzo-quinone
• Diisobutylaluminum Hydride
• 4-Dimethylaminopyridine
• Dimethyldioxirane
• 1-Ethyl-3-(3'-dimethylaminopropyl)carbodiimide Hydrochloride
• N-Iodosuccinimide
• Iodotrimethylsilane
• 2-Iodoxybenzoic acid
• Lithium Aluminum Hydride
• Lithium Diisopropylamide1, 2
• Lithium Naphthalenide
• Manganese Dioxide
• Osmium Tetroxide
• Oxalyl Chloride
• Oxalyl Chloride–Dimethylformamide
• Ozone
• Pinacolborane
• Potassium Hexamethyldisilazide
• Potassium Monoperoxysulfate
• Potassium tert-Butoxide
• Ruthenium(II), Tris(2,2′-bipyridine-κN1,κN1′)-, (OC-6-11)-
• Samarium(II) Iodide
• Scandium Trifluoromethanesulfonate
• Sodium Azide
• Sodium Borohydride
• Sodium Cyanoborohydride
• Sodium Hexamethyldisilazide
• Sodium Hydride
• Sodium Periodate
• Tetrabutylammonium Fluoride
• Tetrakis(triphenylphosphine)palladium(0)
• Tetra-n-propylammonium Perruthenate
• p-Toluenesulfonyl Chloride
• Triethylsilane
• Trifluoromethanesulfonic Acid
• Trifluoromethanesulfonic Anhydride
• Trimethylsilyl Trifluoromethane sulfonate
• Trimethylsilyldiazomethane
• Zinc–Acetic Acid
• List of Contributors
• Index
• End User License Agreement