Julia Olefination

(SET)

Ramberg Backland Olefination

(trans)

Pummerer Reaction

(HEMI THIOACETAL)

Sulfoxide Elimination

(Se does the same)

Allylic Sulfoxide Rearrangement

(Se does the same!)

Barton Dehydroxylation

(removes alcohol)

Dess Martin Oxidation

(alcohol to ketone)

TEMPO-BAIB Oxidation

(alcohol to ketone)

Mitsunobu

(alcohol to ester)

Forms cations in the beta position

(C-Si sigma overlaps with p orbital)

(and alpha anions)

Hydroboration

(addition of C=O across a diene)

Thexyl borane forms 5 mem ring

CO attacks the B

Migration to form 6 mem ring

O attacks B to form 3 mem ring

Migration to neutralise B and form a 5 mem ring

H2O attacks B, standard hydroboration

Brook Rearrangement

(SiR₃ moves to alcohol O^- to be replaced by E⁺)

Reduce things as H^-!

Possible to have H⁺ and H^- in the same reaction...

Ways to remove Si protecting groups?

(3 ways...)

TBAF

Bu₄N⁺F^-

HF, pyrimidine buffer (the classic)

R₃Sn-H

This is mentioned in the course...

Just revise radical stuff... -_-:;

C3, M10 p21 etc.

Fleming Tamao Reaction

(removes silicon)

NO NEED TO KNOW MECH!!!

R--Si(PhMe₂) -> R--OH

Reagents:

Hg(OAc₂) mercury

RCO₃H mcbpa

Retention of configuration

WH: Torquoselectivity in electrocyclic reactions

How do EDG and EWG behave?

EDG rotate outwards

EWG rotate inwards

Normally, electronic effects dominate sterics

WH: Electrocyclic

Nazarov Cyclisation

Double alpha-beta unsaturated carbonyl

Forms pentane

CON under heat and Lewis Acid

WH: Electrocyclic

Ketene Cyclisation

(HARD)

Not [2+2] or stepwise

Draw the orbitals...it's that weird one.

SYN.