Most reagent questions are really workup questions. Read the second step before you commit to a product.
| Reagent | What it does | Works on | Watch out for |
|---|---|---|---|
| NaBH4 | Mild reduction to an alcohol | Aldehydes, ketones | Will not touch esters or carboxylic acids |
| LiAlH4 | Strong reduction to an alcohol or amine | Esters, acids, amides, nitriles | Violent with water — quench carefully |
| DIBAL-H | Partial reduction, stops at the aldehyde | Esters, nitriles | Needs low temperature (−78 °C) |
| PCC | Oxidation that stops at the aldehyde | 1° alcohols | Anhydrous — water pushes it to the acid |
| H2CrO4 (Jones) | Full oxidation | 1° → acid, 2° → ketone | 3° alcohols do not react |
| mCPBA | Epoxidation; Baeyer–Villiger insertion | Alkenes, ketones | Migration follows the more substituted group |
| OsO4 | syn dihydroxylation | Alkenes | Toxic — usually catalytic with NMO |
| O3 | Ozonolysis — cleaves the double bond | Alkenes, alkynes | Workup decides: Me2S → aldehyde, H2O2 → acid |
| BH3·THF, then H2O2/NaOH | Hydroboration–oxidation | Alkenes | Anti-Markovnikov and syn; no rearrangement |
| Hg(OAc)2/H2O, then NaBH4 | Oxymercuration–demercuration | Alkenes | Markovnikov with no carbocation rearrangement |
| H2, Lindlar | Partial reduction to the cis alkene | Alkynes | Poisoned catalyst stops at the alkene |
| Na / NH3(l) | Dissolving-metal reduction to the trans alkene | Internal alkynes | Radical anion mechanism |
| SOCl2 | Swaps OH for Cl | Alcohols, carboxylic acids | Inverts configuration at the carbon |
| PBr3 | Swaps OH for Br | 1° and 2° alcohols | Also inverts |
| NBS | Radical bromination at the allylic or benzylic position | Alkenes, arenes | Low Br2 concentration avoids addition |
| LDA | Bulky strong base — gives the kinetic enolate | Ketones, esters | Use −78 °C for kinetic control |
| RMgX (Grignard) | Delivers a nucleophilic carbon | Carbonyls, epoxides, CO2 | Destroyed by any acidic proton, including water |
| R2CuLi (Gilman) | 1,4-conjugate addition | Enones, acyl halides | Softer than a Grignard, so it adds 1,4 not 1,2 |
Where a reagent has a workup step, the outcome usually depends on it — read the second line of the question before choosing the product.