Topics to Know for the final exam

Key: Square = very important, dot = less important but still good to know

Unit 1 - Molecules and Reactivity

Molecular Structure Be able to identify a carbon as sp3, sp2, or sp hybridized Be able to draw the bonding and non-bonding orbitals for carbons Be able to convert a condensed structure into a line structure

Be able to name alkanes and alkanes Identify an alkene as E (opposite) or Z (same) Be able to predict if a species has a strong or weak dipole (separation of charge) Conformations Understand why ethane prefers being staggered vs. eclipsed, and draw a diagram relating angle vs. energy Be able to do the same for butane comparing the staggered, gauche, and eclipsed conformations Draw a chair conformation, and identify a substituent as either axial or equatorial Be able to draw the result of a ring flip ring flips preserve upedness! Be able to predict which ring flip conformer of a given cyclohexane is more stable (larger groups prefer to be equatorial) Know that t-butyl groups are locking groups they must be equatorial

Stereochemistry Identify all stereocenters in a given molecule Identify a stereocenter as R or S (tiebreaker: element, then # of that element)

Draw the Newman projection looking down any given C-C bond Newman projection for cyclohexanes (see exam 1) Identify a molecule as chiral or achiral Be able to draw the enantiomer (mirror image) for a given chiral molecule Identify molecules with a mirror plane as meso (2+ stereocenters) Identify pairs of molecules as either identical, enantiomers, or diastereomers (stereoisomers that are not enantiomers) Acid/Base Chemistry Know the pkas of: alcohols (acting as acid (15) or base (4)), amines (acting as acid (35) or base (10)), carboxylic acids (5), phenols (10), alkynes (25), alkenes/alkanes (50), enolates aldehydes/ketones (20), ester (25), amides (30), dicarbonyls (10-12) Predict the direction of an acid/base equilibrium Determine if a species is a strong or weak acid based on: element effects (acidity increases to the right and down the PT), resonance stabilization of conjugate base, hybridization (sp > sp2 > sp3), and induction (look for F!)

 Know that everything for bases is the exact opposite as for acids Reaction Coordinate Diagrams Be able to identify high energy intermediates in a reaction (carbocations, radicals), and know that more stable species are more favored at equilibrium Be able to approximate the RCD for a given reaction relative energy of intermediates, reactants, and products (see exam 1) Predict the rate determining step for a reaction (the highest energy barrier) Know that Hammonds Postulate tells us that when comparing high energy intermediates, the most stable is formed fastest

Unit 2 Addition to alkenes and alkynes

Know the mechanism of acid addition to an alkene (e.g. HBr) formation of a carbocation Know Markonikovs Rule (basically that the most stable carbocation is formed) Know the rules for carbocation stability: benzyl, allyl > 3 > 2 > 1 > methyl, and be able to compare carbocations Carbocation rearrangement mechanisms need a driving force Halonium intermediates Be able to predict the regiochemistry of an addition to an alkene i.e. Br2 + H2O Know how to make Markonikov (H2O + H2SO4) and anti-Markonikov (BH3) alcohols from alkenes Know the rest of the alkene reactions from the reaction list Know that terminal alkynes can be converted into aldehydes (BH3) or methyl ketones (HgSO4)

 Know that you can make C-C bonds by doing Sn2 reactions with deprotonated alkynes Be able to selectively reduce an alkyne to either a E (Na, NH3) or Z (H2, Lindlars) alkene Know the rest of the alkyne reactions from the reaction list

Unit 3 Nucleophilic Substitutions and Eliminations

Know the mechanisms of Sn1, Sn2, E1, E2, and E1cb, along with RCDs Know what kind of substrates each reaction works with i.e. no Sn2 on tertiary centers Know that Sn1, Sn2, E1, and E2 reactions do not work on sp2 hybridized carbons Be able to predict which of the above 5 reactions will take place under given conditions Identify good leaving groups Be able to identify a good nucleophile (to the right and down the periodic table) and electrophile Know that adding steric hindrance to a nucleophile makes it more likely to act as a base Know that the most substituted alkene is usually formed in an elimination reaction

Unit 4 Reactions of carbonyl groups

Know which reagents to use to reduce carbonyls to alcohols / aldehydes Know which reagents to use to oxidize alcohols / carbonyls Know how to make and use Grignard Reagents and alkyllithiums (from corresponding alkyl halides)

 Know that cuprates react with acid chlorides only once, whereas Gringards add to acid chlorides twice Know how to make Wittig reagents (treating corresponding halide with PPh3 and then base) Know that the Wittig reaction only works with ketones and aldehydes Reductive amination ketones and aldehydes only best way to synthesize amines from C=O Know the classic addition/elimination mechanism for reactions at esters, acids, amides, and anhydrides, along with other species Know the classic products for the aforementioned reactions Know the mechanism for enolate formation using bases Kinetic (LDA, less subd) vs. Thermo (NaOEt, more subd) enolate Enolate alkylation is a good way to make substituted aldehydes and ketones Aldol reaction enolate alkylation where the electrophile is an aldehyde; classic product is either a 1,3-hydroxycarbonyl or a,bunsaturated carbonyl after E1CB Be able to recognize when you need to use an aldol reaction! Claisen reaction enolate alkylation with an ester, less useful than aldol Acetoacetic ester and malonic ester synthesis best way to make cyclic molecules Decarboxylation of 1,3 dicarbonyls (at least one must be an ester or acid) Know all of the reactions available to you (there are a LOT) Reactivity ordering of carbonyls Acidity of adjacent protons

Unit 5 Electrophilic Aromatic Substitution

 Be able to identify a compound as aromatic (4n + 2 pi electrons), antiaromatic (4n), or nonaromatic. Aromatic compounds must have a cyclic array of p orbitals. Know the standard mechanism of EAS reactions Know all of the EAS reactions available to you Know which groups are o/p directors and which are meta directors Know which groups are activating or deactivating Be able to use EAS reactions in synthesis In general: Draw curved arrow mechanisms for unknown reactions (analyze them based on what reactions you do know) Synthesis what are likely first and last steps? Ranking questions