bootcamp orgo

adding HX to alkene =

mark product + C+ intermed

adding HBr and PEROX to alkene =

antimark product

adding Acid + H2O (2 eq) to alkene

mark product (OH) + this can have rearrangements

1) Hg(OAc)2, H2O, THF / 2) OH- , NaBH4 to alkene =

mark product (OH) + NO rearrangements

(oxymerc-demurc)

1) BH3, THF / 2) perox , OH-, H20 to alkene =

antimark prod (OH)

(hydroboration ox)

acid + ROH (2 eq) to alkene =

ether

mark prod + C+ intermed

adding halogens (Br2) + CCl4 to alkene =

= dihalide + always anti + no rearrange bc no C+ intermed (triangle)

Br2 + H2O(2eq) to alkene

anti prod (Br + OH)

Br2 + ROH

anti (Br + OR)

adding any peroxyacids / MCPBA =

forms epoxide at double bond

adding Nuc- to epoxide under BASIC condns

= Nuc is at less hindered C

adding Nuc- to epoxide under ACIDIC condns

Nuc is at more hindered C

1) OSO4

2) perox(H2O2)

= cis diol (dihydroxide)

1) O3

2) Zn, H20 or DMS ((CH3)2S)

= normal saw

1) O3

2) H2O2 (perox) on a terminal alkene

add OH to each alkene C (one prod COOH and other aldehyde)

1) KMnO4 (hot)

2) Acid (H3O+) to terminal alkene

same as O3/H2O2 but one prod COOH, one prod CO2 (saw)

HIO2 to alkene

same as O3 but forms aldehydes (saws alkene to make aldehydes)

1) KMnO4 (hot)

2) Acid (H3O+) to internal alkene

one prod COOH, one prod aldehyde (saw) (same as O3/perox)

KMnO4 (neutral - no acids) to alkenes

same as OSO4 + H2O2 = cis diol (Baeyer’s reagent)

1) H2

2) Pd, Ni, metal catalyst

to alkene =

reduce to CIS alkane

O3 with internal alkynes

COOH

O3 with terminal alkynes

CO2

1) basic KMnO4, OH-, H2O

2) H2O, H3O+

to alkynes

COOH

H2 + Lindlar’s catalyst to alkynes

reduce to CIS alkane

1) Na OR Li

2) NH3 (I), 78 deg C to alkynes

reduce to TRANS alkane

XS HX to terminal alkyne (like HBr)

= double X mark prod

XS HBr with perox to terminal alkyne

double X antimark prod

XS HX to internal alkyne

2 prods double X mark

XS X2 to terminal alkynes

tetrahalide (double X mark on both alkyne C)

1) H2SO4

2) HgSO4

to terminal alkyne

ketone (mark enol is intermed that goes thru taut)

1) H2SO4

2) HgSO4

for internal alkyne

2 ketones (2 mark enols = taut = 2 ketones)

SiaBH OR BH3THF to term and intern alkynes

antimark enol + aldehyde prods

NaNH2 to terminal alkynes =

acetylide (remove H’s on ends)

2 eq NaNH2 to alkenes

turns alkenes to alkynes

kinetic prod vs thermo product from conjugated dienes

kinetic = quick + most stable at LOW temps (below 40 deg C)

thermo = slow + most stable overall (high temps) (most subbed/internalized alkene)

which is more reactive aldehyde or ketone

aldehyde bc less sterically hindered

aldehyde /ketone +

1) OR-, HOR

2) H2O, H30+ (BASIC)

= hemiacetal / ketal (reduce to OH + add OR group)

aldehyde/ketone +

1) H+

2) HOR (Acidic)

acetal / ketal = reduce to two OR groups

what does NABH4 do to ketones and aldehydes

ketone = reduce to 2° OH

aldehyde = reudce to 1°OH

what does LiALH4 do ?

reduce everything to OHs including COOH (to 1°OH) + esters (much stronger than NaBH4)

what are good protecting groups for ketone/ald C=O groups ?

ketals

aldehydes/ketones + 1° amines

1) H+

2) H2NR

= imines (Schiff bases) (CNR’) O switch places with amine

ald/ket + 2°amines = ?

= alkene + amine (enamine) (double bond moved to next C)

asymmetric ketone + 2° amine =?

alkene + amine (antiZaitsev prod = less subbed = major)

what do Grignard reagents + organolithium reagents do?

add carbons when reducing OH

ketone/ester + Grignard reagent

1) RMgX, Et2O

2) H+

3°OH

aldehyde + grignard reagent (RMgX , Et2O/H+) = ?

2°OH

aldehyde/ketone + ylide- =?

C=O to C=C bond (Wittig rxn)

O and C switch places and OPPH3- is the second product)

how to make ylide -?

alkyl halide +

1) PPH3

2) BuLi (SB) = deprotonates

what do michael additions do? (1,4-addns)

exterior C=C attack on the Beta C=C(not direct attack) and adds a nuc there

what is an alpha carbon?

carbon that is one posn away from carbonyl carbon

which nucs prefer Mike addn

weaker nucs =

CN-

HNR2

R2CuLi (only 1 R group added)

bulky(-)

which nucs prefer direct 1,2-addn ?

H-, Grignards, organolithiums =

NaBH4, LiAlH4 (H- source)

RMgX, RLi

geminal vs vicinal dihalide

geminal = X’s bound to same C (gem = jammed to one C)

vicinal = X’s next to each other

IR peak for carbonyl C

1750 ± 50

IR peak of 1600-1700?

C=C OR C=N

IR peak of 3000 large, broad U ?

OH stretch

IR peak of 3000 with overlapping C-H peak?

COOH

IR peak of 3200-3500 , one SHARP peak

N-H

IR peaks of 3200-3500 with two peaks?

NH2

med IR peak of 2200?

nitrile (CN)

IR peaks in 1500-1600 & 1300-1400 (vampire teeth)?

NO2

what happens to the wave # and the bond enery movement as you move left on the IR spectrum?

further left = incr wave # = incr bond energy movement

what type of peaks do amines vs amides have?

amines = sharp peaks

amides = shark peaks w c=o

purpose of UV-vis spec?

to analyze comps w conjugated dooble bonds

purpose of mass spec?

compound’s mass

On a mass spec , what type of peak is the most stable/abundant ?

tallest peak = base peak = most stable = most abundant

mass spec for Br?

2 twin peaks 1:1 ratio (156 + 158)

mass spec for Cl?

2 peaks at 112 + 114

3:1 ratio

mass spec for Br + Cl tg?

3:4:1 ratio

m + m+2 + m+4 (190, 192, 194)

mass spec for Cl+Cl?

9:6:1 ration

how to find degree of unsaturation?

C - (H/2) - (X/2) - (N/2) + 1

what happens when you go more left/more right on 13-CNMR spec?

more left = more (+) charge

more right = more (-) charge (shielded)

(THIS IS THE SAME W HNMR SPEC)

CNMR peak for 160-180 ppm

carbonyl C (esters, amides, COOHs)

CNMR peaks that are greater than 200 ppm

aldehydes + ketones

HNMR peak of 1-4 ppm

alkane H (ex: CH3, CH, CH2, etc.)

HNMR peak of 4-6 ppm

alkene

HNMR peak of 6-8 ppm

ring H

HNMR peak of 9-10 ppm

aldehyde H

HNMR peak of 11-14 ppm

COOH

HNMR peak of 1-5 ppm ?

OH or NH

what is H splitting in proton (H) NMR ?

counting neighboring H’s

enantiomers vs diastereomers

enantiomer = nonsuperimposable + mirror img (& opposite R, S configs)

diastereomer = nonsuperimposable + not mirror img

both are stereoisomers

what is the priority for chiral centers?

highest priority = highest atomic #

lowest priority ALWAYS dash (away from you)

how to find # of possible sterocenters?

2^n

n = # of stereocenters

3 types of diastereomers

1) cis trans isomers of rings

2) cis/trans/E/Z isomers of alkenes (molecs w no stereochem)

3) stereoisomers w multiple stereocenters that dont have opposite R, S configs

3 types of ACHIRAL molecs

1) racemic mixtures (50/50 mix of 2 enantiomers)

2) molecs w no stereochem/stereocenters/cistrans

3) meso comps (molecs w line of symmetry + 2 stereoceners)

what is optical activity

chiral, nonmeso comps that can rotate light

D = clockwise

L = CC

which are harder to separate, enantiomers or diastereomers?

enantiomers

when can single bonds NOT rotate?

when in rings

fischer projections horizontal vs vertical

horizontal = toward you

vertical = away

D sugars vs L amino-acids

D sugars = naturally occurring sugars

L sugars = naturally occurring amino acids

CA vs CB

CA = product comes from BASE (has (-) charge

CB = product comes from ACID (has (+) charge + H)

when are CBs and CAs stable?

the stronger the acid/bases are

ROH , H2O, H3O pka’s?

ROH + H2O = both pka 16

H3O = pka 2

COOH and NH4 pka’s

COOH = pka 5

NH4 = pka 10

how to sort A/B strength using CARDIO?

1) Charge = more (+) charges = more acidic (and (-) charges more basic)

2) Atom = across row = more EN = more acidic ; down group = incr size = incr acidicty

3) Resonance = more stable CB = stronger acid (replace reactant H w (-) and ask urself if it has any res)

4) Dipole Induction (tug-of-war)

• withdrawing groups incr acidity (F, CL, Br, I)

• donating groups decr acidity (C or H groups)

  • these are the oppsite when ranking basicity

5) Orbital hybridization = incr S-character = incr EN = incr acidicity (sp = 50% s, sp2 = 33%, sp3 = 25%)

how to predict structures of amino acids using pH

if pka < pH = deprot (o- for oxygen, neutral N for nitrogen)

if pka > pH = prot (OH for oxygen, NH3+ for nitrogen)

at pH 7.4 = neutral

how to name ethers?

name the two alkyl groups on each side and tack on ether at the end

how to name esters

alkyl group + oate