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Gabriella Fiorino
Reagent List
Note: This list may not encompass everything done in your specific class so do NOT just use this to study. Also, some reagents may go beyond what you learned, so this is only meant as a guide.
Study well my friends! You can do it! :D
Polar Protic and Aprotic SolventsNote: These are just a few popular examples of the solvents. It is helpful to not only recognize the names of the solvents, but also understand what makes something protic and what makes something aprotic.
Polar aprotic solvents cause reaction to occur via Sn2: DMSO DMF (dimethylformamide) CH3CN (acetonitrile) HMPA (hexamethylphosphoramide)
These solvents do not form hydrogen bonds
Polar protic solvents cause reactions to occur via Sn1: EtOH NH3 (ammonia) Acetic acid MeOH (Methanol) H2O HCO2H (Formic acid)
These solvents can form hydrogen bonds
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Sn1 Reacts in multiple steps Watch for hydride/methyl shifts! Reagents: Weak nucleophiles Solvents: Polar Protic React only on secondary or tertiary structures Forms racemic mixture (product plus its enantiomer)
Sn2 Reacts in 1 step (concerted reaction) No hydride/methyl shifts! Reagents: Strong nucleophiles Solvents: Polar Aprotic React only on secondary or primary structures Causes inversion of configuration
E1 Reacts in multiple steps Watch for hydride/methyl shifts! Only occur with weak Nu/bases on Secondary (only if using H2SO4) or Tertiary structures
E2 Reacts in 1 step No hydride/methyl shifts
Sn1, Sn2, E1, E2 Review
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Source: Klien, D.R. (2015). Organic Chemistry: 2nd Ed. Wiley: NJ. Print.
Examples of substitution and elimination reagents. Only examples and not a comprehensive list. Understand what makes something strong/weak Nu or base.
Nucleophile only examples: NaX (X = halogen)
o i.e. NaCl NaSH
Base only reagent examples: NaH NaNH2
Strong Nu/strong base reagent examples:
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Tert-butoxide NaOH KOH
Weak Nu/Weak base MeOH EtOH H2O
Make OH a good leaving group
TsCl/Pyridineo Turns OH OTs
H2O or H3O+ or Concentrated H2SO4 or HX (X = halogen)o Turns OH H2O
PBr3
o Exchanges OH for a Br SOCl2
o Exchanges OH for a Cl POCl3/pyridine
o Turns OH alkene
Syn Addition
Catalytic hydrogenation o H2 with a metal (i.e. Pt, Pd, Ni, etc.)
Hydroboration oxidation o Anti-markovnikovo Can do enol keto tautomerization (Turns enol keto)o Reagents:
1) BH3, THF 2)H2O2, NaOH 1)9 – BBN 2) H2O2, NaOH
Anti-Addition
Halogenationo i.e. Br2
Halohydrino Br2 or Cl2 followed by H2O
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o OH goes to more substituted area and halogen to less substituted area
Depends: Dihydroxylation
o Alkene diol Anti-addition reagents
MCPBA and peroxyacetic acid (RCO3H) paired with NaOH (or KOH) o First, MCPBA or other peroxyacetic acids form epoxideo Then NaOH opens epoxide, creating trans diol.
Syn – Addition reagents Form syn diols
o OsO4 with Na2SO3/H2O or HaHSO3/H2Oo KMnO4, NaOH (or KOH), H2O
Often in cold temperatures
Markovnikov H3O+
o Adds OH to more substituted area Dilute H2SO4 (also written as H2SO4, H2O)
o Be careful! Concentrated H2SO4 does E1/makes OH a good leaving group. o Dilute H2SO4 adds OH to more substituted area
HXo X = halogeno Add halogen to more substituted area
Oxymercuration – demercuration o 2 steps:
1) Hg(OAc)2 with nucleophile NaBH4
o Adds OH to more substituted area
Anti – Markovnikov
H2O2 (can also be written as ROOR) Hydroboration oxidation (BH3, THF and 9 – BBN)
o Also does syn addition or enol keto tautomerization.
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Enol keto tautomerization reagents Turns enol keto
o BH3, THFo 9-BBNo HgSO4, H2O, H2SO4
Reducers
H2 with metal catalyst (i.e. Pd, Pt, Ni, etc.)o Complete reduction o Alkyne alkene alkaneo Aldehyde primary alcoholo Ketone secondary alcohol
H2/Lindlar’s catalysto Alkyne cis alkene
NaNH3
o Alkyne trans alkene
LiAlH4/H3O+
o LiALH4 is also called LAH (lithium aluminum hydride) o Fully reduceso Primary carbonyl aldehydeo Secondary carbonyl ketone o Reacts with all carbonyls
NaBH4 with MeOH or H2Oo Fully reduces o Primary carbonyl aldehyde o Secondary carbonyl ketone o Reacts with carbonyls except for esters and amides
Oxidizers
KMnO4 with NaOH (or KOH), H2O or o In cold temperatures o Alkene syn diol
OsO4 with either NaH5O3, H2O or NMO
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o Same as KMnO4 with NaOH, H2O, cold
MCPBA and other peroxyacids (RCO3H)o Alkene epoxide o Followed by NaOH trans diol
O3, DMS or O3, Zn, H2Oo Alkene ketone and/or aldehyde
O3, H2Oo Alkene or alkyne COOH o If reacting with 1 carbon CO2
PCCo Primary alcohol aldehyde o Secondary alcohol ketone
K2Cr2O7, H2O, H2SO4 or CrO3, H3O+
o Of course, could use Na2Cr2O7 instead of K2Cr2O7
o Primary alcohol COOHo Secondary alcohol ketone
NOTE: secondary alcohols ketones but primary alcohols are what differ per reagent
1)Mg 2) CO2 3) H3O+ o React with alkyl halide COOH o First step is a Grignard reaction (intro to Orgo 2!)
Radical reactionsNBS:
Radical bromination Add bromine to allylic carbon (the carbon adjacent to the double bond
Br2 with light: Add bromine to most substituted area Very selective
Cl2 with light Less selective Adds to less substituted area
Remember the most important rules to this course:
Gabriella Fiorino
o Negative things go to positive things (draw arrows from nucleophile to electrophile)o Count your carbonso OH is a bad leaving groupo Watch for hydride/methyl shifts!o Study a little bit each day. Chemistry takes practice. Do not give up and do not panic! :)
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References: Klien, D.R. (2015). Organic Chemistry: 2nd Ed. Wiley: NJ. Print.