Organic Chemistry Final

H-Br

H-X addition to alkenes:

1) adds to resonance stabilized carbocation first

2) adds to more stable carbocation

3) look out for EWG’s (they’re less stable)

H₂SO₄, H₂O

Addition of H₂O:

1) Adds to resonance stabilized carbocation

2) adds to more stable carbocation

H₂SO₄, R-OH

1) Adds to resonance stabilized carbocation

2) adds to more stable carbocation

H-A

CH₂N₂, Light

CHCl₃, KO^tBu

CH₂I₂, Zn(Cu)

mCPBA

Epoxide Opening:

1. NaOR

2. H₃O⁺

1) Nuc adds to less substituted carbon

2) Inversion of Stereochemistry at a chiral center

Epoxide Opening:

1) LiAlH₄

2) H₂O

Epoxide Opening:

1) R-MgBr

2) H₃O⁺

Epoxide Opening:

1) R-Li

2) H₃O⁺

→ backside attack, makes enantiomers

Epoxide Opening:

H₂SO₄, CH₃OH

1) Add the nucleophile to the more substituted side

2) invert stereochemistry

Br₂

Cl₂, H₂O

→ OH is added to the more substituted side

1) Hg(OAc)₂, H₂O

2) NaBH₄

→ OH is added to the more stable side

1) BH₃

2) H₂O₂, NaOH

1) OH is added to the less substituted side

2) Syn addition of H & OH

1) OsO₄

2) NaHSO₃, H₂O

→ Syn addition of OH

NaIO₄

→ Carbon between OH becomes H

→ OH needs to be syn

1) O₃

2) Zn

1) O₃

2) H₂O₂

Pd, H₂

Pd, H₂, Quinoline

→ makes cis alkenes

Na or Li, NH_3(l)

→ makes trans alkenes

1) LiAlH₄

2) H₃O⁺

In an Aldehyde/Ketone:

1) R-MgBr

2) H₃O⁺

1) Na-Terminal Alkyne

2) H₃O⁺

NaCN, HCN

→ works for both aldehydes and ketones

NaOR, ROH

PH₃P⁺- ^-CH₂

→ Unstabilized Ylide = Z-Alkene

→ Stabilized Ylide = E-Alkene

1) NaOCH₃

2) aldehyde/ketone

HCl, H₂O

HCl, EtOH

→ works as a protecting group for aldehydes/ketones

cat. HCl, R-NH₂

→ can also be cat. acetic acid

→ can be used on both aldehydes and ketones

cat. HCl, Secondary Amine

H₂N-R

1) acetic acid

2) NaBH₄

3) H₃O⁺

cat. acetic acid

H₂N-R

NaCNBH₃

H₂N-NH₂

KOH, H₂O

Heat

1) LDA or NaOH

2) R-Br

NaOH, H₂O

or

HCl

NaOH, heat

NaOMe, CH₃OH

→ More substituted side

1) LDA, -78ºC

2) H₃O⁺

→ Less substituted sidee

Explain 1,2 vs. 1,4 addition

→ this occurs in alpha, beta unsaturated carbons

NaOH, EtOH

NaOH, EtOH, heat

Reduction: Catalytic Hydrogenation (H₂, Pd/C/Pt)

→ only reduces aldehydes, but not ketones

CrO₃, H₂SO₄, H₂O

→ no reactions for 3º -OH

→ no new carbons added

1) (COCl₂), DMSO

2) NEt₃

→ no reaction for 3º -OH

DMP

→ does not work for 3º -OH

TMSCl

TBAF

→ protecting group for alcohol

Mg

1) Mg

2) CO₂

3) H₃O⁺

→ added new carbons

SOCl₂

C.A.A.K.E. C.A. A.C.

Ester

NaOH, H₂O, HCl

Ester

H₂SO₄ or H₃O⁺

R-OH

Ester

R-NH₂, heat

DCC, R-NH₂, NEt₃

Amide, H₂O

HCl or NaOH, heat

1) LiAlH₄

2) H₃O⁺

1) NaBH₄

2) H₃O⁺

→ reacts with ketones and aldehydes, but not esters

1) DIBAL-H

2) H₃O⁺

1) R’MgBr (excess)

2) H₃O⁺

Amide:

1) CH3-MgBr

2) H₃O⁺

1) NaOEt, EtOH

2) H₃O⁺

1) NaOCH₃, CH₃OH

2) H₃O⁺

Claisen Condensation

1) NaOH

2) Br-R

1) H₂SO₄, H₂O

2) heat

Cl₂, FeCl₃

Br₂, FeBr

HNO₃, H₂SO₄

SO₃, H₂SO₄

→ we need to do carbocation rearrangements!

Positions of Aromatic Rings, Ortho/Para Directors, Meta Directors

Electron Donating Groups are Ortho/Para directors

Electron Withdrawing Groups are Meta directors

cat. Pd, H₂