ucfstudyunion.files.wordpress.com · Web viewAnti-markovnikov Can do enol keto tautomerization (Turns enol keto) Reagents: 1) BH 3, THF2)H 2 O 2, NaOH 1)9 – BBN2) H 2 O 2, NaOH

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.

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

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

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: 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 H2Oo 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

HX

o 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.

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 reduces carbonyls alcohols o Reacts with all carbonyls

NaBH4 with MeOH or H2Oo Fully reduces carbonyls alcoholso 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 NMOo 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!)

Remember the most important rules to this course:

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.