Exam 1 Review Flashcards
Thermodynamic enolates from ketones
One can generally use the rules governing alkene stability to predict the thermodynamic enolate
LDA cold forms thermo or kinetic?
Kinetic micheal =1,4
acidic conditions mostly favor thermo or kinetic
thermo
Micheal Addition
-LDA cold
enolate attacking alpha beta unsaturated
-initial step is a 1,4 (beta position) addition to an appropriate carbonyl
-Upon completion of the additional subsequent aldol condensation can occur if the conditions are right
Claisen Condensation
Direct 1,2 addition to an ester
Conjugation
-More conjugation=more stability
-The condensation part of an aldol sequence benefits from increased conjugation
-Conjugation increases (if applicable) when push/pull systems are in place
push/pull systems
a connected pair of resonance acceptors and donators
Water solubility
more charged/able to be protonated is more soluble
where does kinetic add
less substituted side
what breaks conjugation
sp3 gates
something in meta position can’t dump over
Greater selectivity for kinetic position
more sterics
Enolates delta g double dagger
kinetic has lower
thermo has higher due to sterics
Aldol condensation sans heat
the compound being produced has increased conjugation (the condensation occurs spontaneously)
stronger the acid
most destabalized positive charge
Stronger the base
more stabalized
