Organic Chemistry 2 General

sad :(

What reagents can be used to reduce alkenes? What kind of addition is this?

Hg(OAC)2, H2 with Pd/C catalyst

What is markovnikov’s rule? What mechanism causes the opposite to occur?

H adds to the least substituted carbon, Hydroboration

What increases the formation of the anti-Markovnikov product in hydroboration? Which are common reagents to do this?

Steric hindrance/bonds to things besides H, 9-BBN and (sia)2BH

Which reagent creates an epoxide over an alkene? What is it normally, and what does it become when deprotonated?

m-CPBA, electrophilic oxygen, becomes nucleophilic

Which reagent oxidizes BR3 into a borate anion? What does this result in?

Hydrogen peroxide and sodium hydroxide, forms boric acid and alcohols (with acid workup)

Which alkenes react with which m-CPBA?

electron rich alkenes react with m-CPBA, electron poor alkenes react with m-CPBA treated with base to deprotonate it

What is the main reactant in Gabriel synthesis? What does Gabriel synthesis do?

Hydrazine H2N-NH2, removes a protecting group from nitrogen (1,2 addition to a carbonyl)

What’s an easy way to get an alcohol to become a leaving group?

Tosyl or mesyl chloride

Which molecules are always a base?

NaH, KOtBu, LDA, Et3N, iPr2NET

Which molecules are always nucleophiles?

RNH2, R2NH, H2O, ROH

Which molecules can be both bases and nucleophiles?

MeO-, EtO-

pKa of acetic acid, what functional group is it?

4, carboxylic acid

pKa of methanol

16

pKa of phenol

10

pKa of a secondary amine (or just amine?)

36

pKa of an imide (ish) what groups make up an imide?

14, N next to two carbonyl groups

pKa of butyl lithium, what is it often used for?

50, enolate formation

pKa of di-isopropylamide

36

pKa of phenyl

33 ish

First cyclic intermediate formed in ozonolysis name

molozonide

Second cyclic intermediate formed in ozonolysis

ozonide

What product does hydroboration always create?

anti-Markovnikov product

Conditions to form an acetal

dry acid

conditions to lyse an acetal

wet acid

Type of nucleophile that favours 1,4 addition (conjugate). What directing factor causes this?

soft nucleophile, orbital overlap

Type of nucleophile that favours direct addition to carbonyl, what directing factor causes this?

hard nucleophile, electrostatic interactions

pKa of a benzene ring

about 40

What is the P in clogP and what does c stand for? What does it determine?

Partition coefficient, calculated, amount of drug in octanol and in water.

What is the rule of 3 used for, and what is the rule of 5 for?

Fragment discovery, drug final structure guiding lines

Partial agonist

A drug that binds to a receptor but does not produce the full biological response of an agonist

antagonist

A drug that binds to a receptor but does not cause biological activity. Also blocks natural ligand/agonist from binding. NONZERO ACTIVITY

inverse agonist

Binds to a receptor and stabilizes the inactive form, removing background activity (close to zero activity)

Pharmacokinetics

The properties of a drug relating to dispersal, metabolism, solubility, etc.

Pharmacodynamics

Properties of a drug relating to binding and activity.

What is an effect of reducing the number of rotatable bonds for a drug?

Creates fewer conformations, meaning that the entropic penalty for binding is reduced, and affinity for binding increases.

parallel synthesis, advantages?

Creating drug targets through simultaneous reaction of different starting materials with the same reaction sequence, using the same reagents for each (diff starting materials tho)

Advantages: nominally pure in each tube, and is rapid for generating compound libraries.

What does chirality do for drugs?

targets are inherently chiral, and if enantiomers are introduced, it is likely they will have different affinities.

Main effects of longer alkyl chain on drug oral bioavailability

Increase in lipophilicity decreases aqueous solubility, and fat globules will dissolve it more. Also decreases in molecular rigidity leads to decreased membrane permeability (requires fixed conform, higher entropic penalty if more rotatable bonds)

Vinylogy

Transmission of electronic affects across a conjugated system, eg carbonyl carbon is electrophilic, so is the beta carbon (c-c-C)

What determines the reactivity of an alkene?

Electron density, EWGs reduce reactivity

What class of reagent is m-CPBA? What is useful about it?

Per-acid, very unstable O-O single bond wants to break

At neutral, which site does the nucleophile attack when ring opening an epoxide?

Least hindered

In acidic conditions, which site does the nucleophile favor?

Most stable carbocation

What is the sole use of OsO4? Is it stereochemically selective?

Dihydroxylation of alkenes, yes, always syn addition

What can reduce alkynes to alkanes, and how do you reduce it only to alkene?

Pd/C, Lindlar’s Catalyst (poisoned)

Alkyne to alkene reduction with the trans product?

Dissolving metal reaction Na, NH3

What does oxymercuration of an alkyne lead to?

Enol which tautomerizes to ketone

Results of hydroboration of an alkyne, alkene? What kind of alkyne/ene is this mostly used for? What reagents are needed in the two steps?

Enol → aldehyde, alcohol, terminal, 9BBN, then H2O2 and NaOH