orgo prelim 3 reactions

alkene + HX

H on one C, X on other

markovnikov approved

alkene + H2SO4

OH on one C, H on other

markovnikov approved (OH on more sub C, H on less)

alkene + BH3•THF + NaOH + H2O2

OH on less sub C, H on more sub C

anti-markovnikov

alkene + X2

X on each C, anti addition

alkene + H2 + Pd/C or Pt/C or Ni or RH

goes to alkane, another H on each C

syn addition, makes racemic mix

alkene + MCPBA

makes epoxide (triangle across C-C with O)

syn addition

epoxide + acid + water

each C of the ring gets its own OH

nphile attacks MORE sub C first, anti addition

epoxide + base (like OCH3 or K❤︎⁠CN)

less sub C gets the base (OCH3 or CN), more sub C gets the OH

nphile attacks LESS sub C, anti addition

alkene + OsO4 and H2O2 or NMO

an OH for each C of the alkene

cis syn addition, racemic

alkene + KMNO4 + H2O + OH

an OH for each C of the alkene

cis syn addition, racemic

alkene + HG(OAc)2 + H2O + NaBH4

OH on more sub C, H on less

markovnikov approved

alkene + X2 + H2O

OH on more subbed C, X on less

anti addition, racemic

…kinda markovnikov coded

alkene + O3 + (CH3)2S

cut double bond, cauterize each wound w/ a double bond O

don’t mess w/ other parts

this is workup!

alkene + O3 + H2O2

cut DB, cauterize each wound w/ a double bond O, then an H on the less sub C turns into an OH too

this is NOT workup! DO mess with other parts.

alkyne + NaNH2 + [chain]-X

[chain] attaches to end of alkyne, replaces its H, the X is long gone.

alkyne + X2 (1 equivalent)

alkene w/ an X on each C

alkyne + X2 (>1 equivalent)

all the way to alkane, two X’s on each C

alkyne + H-X (1 equivalent)

alkene: X on more sub C, H on less

markovnikov approved

alkyne + HX (>1 equivalent)

alkane: both X’s on more sub C, two H’s on less

markovnikov approved all the way

alkyne + H2 + Pd/C

alkane, two more H’s on both C’s

alkyne + H2 + lindlar + pyridine

cis alkene, one H on each C

alkyne + Li or Na + NH3

trans alkene, add H on each C but like. transly.

alkene + carbene

cyclopropane, triangle across C-C with carbene sticking out on top

alkyne + Hg(2+) + H2O + H2SO4

no more triple bond. DB O on the more sub C, two H’s on the less.

disubbed alkynes make a mix, =O can come out of either side.

markovnikov approved

alkyne + [loss]-BH2 + THF + H2O2 + -OH group

this is hydroboration oxidation

no more alkyne. DB O out of the start of it, turn rest into alkane

enol intermediate: OH goes on less sub C, H on more (anti-markovnikov)

alkyne + Sia2BH + H2O2 + -OH group

this is hydroboration oxidation.

no more alkyne. DB O out of the start of it, turn rest into alkane

enol intermediate: OH goes on less sub C, H on more (anti-markovnikov)

alkyne + 9-BBN + H2O2 + -OH group

this is hydroboration oxidation.

no more alkyne. DB O out of the start of it, turn rest into alkane

enol intermediate: OH goes on less sub C, H on more (anti-markovnikov)

alkene + HBr + O-O

Br on less sub C, H on more sub C (evil evil peroxides)

anti-markovnikov

Initiation

Evil evil peroxides crash out and take out bystanders with it

R-O⋅ + H-BR = R-OH and new Br⋅ (the new evil one)

Propogation

new evil radical attacks alkene, evil Br now satisfied but other C of the alkene is now evil

evil Br adds to LESS SUB C to form more stable radical

anti-markovnikov!

Termination

rad + rad = no more rads

alcohol + HX + water

this is protonation.

replace the OH with the X.

(the O attacked the H to make water, good leaving group)

alcohol + H3PO4

will make alkene adjacent to where OH was

major product will be more subbed alkene

alcohol + H2SO4

will make alkene adjacent to where OH was

major product will be more subbed alkene

alcohol + tosylate + pyridine

replace the H of the alcohol with tosylate, also makes [pyridine]-H byproduct

retains stereochem

alcohol + mesylate + pyridine

replace the H of the alcohol with tosylate, also makes [pyridine]-H byproduct

retains stereochem

alcohol + SOCl2 + pyridine

replace the -OH with a Cl, also invert stereochem (swap the new Cl and H around)

alcohol + PPH3Br + more Br- + DMF or DMSO solvent

replace OH with Br, also invert stereochem (swap the new Br and H around)

2° alcohol + CrO3-H2O + acid

completely take off the -OH and an H from that same C. replace with double bond O.

also makes OH-Cr-OH with another =O out of the Cr as a byproduct too.

1° alcohol + CrO3-H2O + pyridine + HCl + PCC or DCM

this makes an aldehyde. completely take off -OH and an H from that same C. replace w/ double bond O

1° alcohol + CrO3 + H2O

this makes a carboxylic acid. take off both H’s on the C, replace with an =O. keep the -OH on.

1° alcohol + KMnO4 + H2O

this makes a carboxylic acid. take off both H’s on the C, replace with an =O. keep the -OH on.

thiol (R-SH) + HNO3 + H2O

replace the S’s H with an OH. stick two =O on the S too.

thiol (2 equivs) + Br2 (1 equiv)

this makes a disulfide. take off the H, replace it with a second thiol: R-S-S-R

alcohol + NaH → + H2 + RCH2X

take off H of alcohol. replace with CH2R (its X is gone)

ROH + NaH → RO → RO + H2 + RCH3X = RO-CH2-R

i guess the CH3X’s R is optional. this makes an ether!

thiol + NaH + H2 + RCH2X

take H off thiol, replace with CH2R (its X is gone)

alkene + CH3OH (need an alkyl group on the alcohol) + Hg(OAc)2 + NaBH4 + -OH

CH3OH on more sub C, H on less sub C (replace the HgOAc that went on it)

anti-markovnikov

ether (R-O-R) + HI (acidic conditions)

Give the R from ether to I, the other R still has its O but add an H to make an OH on that R

O attacked the H of HI. this makes two of R-I and an H2O

alkene + Br2 + H2O + NaH or NaOH

makes epoxide

epoxide + grignard reagent (like R-MgBr) + any acid

attack epoxide at the hip to where MgBr was on its R, ring opens to have an OH on the opening hinge. also makes H2O

epoxide + H3O + H2O

an OH on each C of the triangle base.

this makes a trans diol! one OH goes forward, other goes back

alkene + OsO4 + MnO

an OH on each of the C’s, now an alkane.

this makes a cis diol! racemic! both OH’s are either forward or back

H5IO6 or HIO4 + a glycol (has two OH’s)

break the bond between the C’s that have OH’s. on each wound, put a =O facing each other.

cis alkene + X2 + MeOH

OMe on one C, X on other

if starting material is cis, final will be trans. vice versa