Orgo Exam II Reactions

Ch.12 - Ch.17 (beginning)

Hydrohalogenation (anti Cl and OH)

Cl₂, H₂O

Syn Hydrogenation (stronger one)

Pd/C, H₂

Anti Dibromination

Br₂, CCl₄

Anti Dichlorination

Cl₂, CCl₄

Less Hindered Face Epoxidation

RCO₃H (ex. MCPBA)

Hydroboration Oxidation (Anti-Markovnikov, less bulky)

1) BH₃, THF 2) H₂O₂, NaOH, H₂O

Dichlorocyclopropanation

KOtBu, CHCl₃

Oxymercuration Demurcuration, for OH addition with no carbocation rearrangement

1) Hg(OAc)₂, H₂O 2) NaBH₄, NaOH, H₂O

Antimarkovnikov Bromination

HBr, ROOR

Syn Dihydroxylation

1) OsO₄, H₂O₂ 2) tBuOH

Anti ether and bromination

Br₂, CH₃OH

Ozonolysis

1) O₃, CH₂Cl₂ 2) DMS

Hindered Face Epoxidation

1) Br₂, H₂O 2) NaOH

Markovnikov Hydration

H₂O, H₂SO₄ (cat.)

Ring Closing Metathesis (RCM)

HGII (Hoveyda-Grubbs catalyst II)

Markovnikov Monochlorination

HCl

Markovnikow Hydrobromination

HBr

Markovnikov Hydrochlorination

HCl

Syn Cyclopropanation

Zn/Cu, CH₂I₂

Oxymercuration Demurcuration, for ether addition with no carbocation rearrangements

1) Hg(OAc)₂, CH₃OH 2) NaBH₄, NaOH, H₂O

Deprotonate an Alkyne

NaH

Double Elimination to Form Alkyne

NaNH₂ (excess)

Grignard an Alkyne

EtMgBr

Alkyne to Alkene Syn Hydrogenation

H₂, Lindlar’s cat.

Alkyne to Alkene, TRANS

1) Na^O, NH_{3 (l)} 2) H₂O

Viscinal Dihalogenation (sometimes tetrahalogenation)

X₂, LiX, AcOH

Terminal Alkyne to Aldehyde

1) (Bulky)₂BH, THF 2) H₂O₂, NaOH, H₂O plus tautomerization

Internal Alkyne to Ketone

HgSO₄, H₂SO₄, H₂O plus tautomerization

Internal Alkyne to Ketone

1) BH₃, THF 2) H₂O₂, NaOH, H₂O plus tautomerization

Geminal Dihalogenation Dihydrogenation

HX (excess)

Primary or Secondary OH to Br

PBr₃

Primary or Secondary OH to Cl

SOCl₂, Pyridine

Heck Reaction

Aryl or Vinyl Halide + Alkene, Pd(OAc)₂, PR₃, NEt₃

Suzuki Reaction

Aryl or Vinyl Halide + Boronate Ester (Alkyne + Catecholborane), Pd(PPh₃)₄, NaOH, heat

Sonogashira Coupling

Aryl or Vinyl Halide + Alkyne, Pd(PPh₃)₄, CuI, NEt₃