reagents

HX

x = Br, Cl, etcs

alkene; bind to the most sub carbocation (resonance wins out all)

H₂SO₄ with H₂O

H₂SO₄ with OR

alkene; OH or OR binds to the most sub carbocation

CH₂N₂

alkene; forms cyclopropane

CH₂I₂ + Zn (Cu)

alkene; forms cyclopropane

CH₂Cl₂

alkene; cyclopropane with two Cl groups

H₂SO₄ with H₂O or OR

epoxide; proponate O in epoxide to OH+, and the H₂O / OR adds to the most sub carbon to then open the epoxide

1. -Nuc or Nuc

2. H₃O+

epoxide; attacks the least sub carbon of the epoxide, and the O- from epoxide opening will grab a H

X₂

alkene; X makes a triangle, and then the second X attacks most sub carbon to break the triangle

if cis alkene → X are opposite stereochem

if trans alkene → X are the same stereochem

mcPBA

alkene; creates an epoxide

if multiple alkenes, choose the one away from EWG or closer to EDG

1. Hg(OAc)₂, H₂O

2. NaBH₄

alkene; OH added to the most sub carbon

1. BH₃ or B₂H₆

2. H₂O₂, NaOH

alkene; H added to the most sub alkene, BH₃ (will turn into OH from step 2) added to the least sub

added syn

1. OsO₄

2. NaHSO₃, H₂O

alkene; syn addition of OH

1. O₃

2. Zn or PPh₃

alkene; it breaks to form aldehydes

1. O₃

2. H₂O₂

alkene; it breaks to form carboxylic acids

NaIO₄

1,2 diol OH; break the carbon bond between the OH’s; if 2° alc, then aldehyde; if 3° alc, then ketone

1. Pd

2. H₂

alkene; reduces it to hydrogens

nitro group; reduces it to NH_x

aldehyde;

Pd on quinoline BaSO₄

H₂

triple bond; reduces it to a cis alkene

Na or Li

NH₃

triple bond; reduces it to a trans alkene

1. NaBH₄

2. H₃O+

aldehydes or ketones; reduces C=O to OH and H

1. LiAlH₄

2. H₃O+

aldehydes or ketones; reduces C=O to OH and H

RM

M = MgBr, Li

aldehydes or ketone; reduces C=O to OH and R attached to organometallic

1. Na alkyne

2. H₃O+

aldehyde or ketone; adds terminally to reduce C=O to OH and alkyne

NaCN

aldehyde or ketone; adds to the C=O to reduce it into OH and CN

NaOR

ROH

aldehyde or ketone; C=O reduces to OH and OR

PPh₃ + RLg

NaH

- on the carbon next to + PPh₃

- +PPh₃

or ketone; - carbon attacks C=O and the O attacks the + PPh₃ to form a box that makes an alkene

• if unstabilized ylide, Z alkene

• if stabilized ylide, E alkene

NaOCH₃

PPh₃ ylide; removes H to make - on carbon next door

aldehyde or ketone; OCH₃ attacks C=O to make hemiacetal (OH with the OCH₃)

HCl (acid catalyzed)

aldehyde or ketone plus another OH group; proponates O in C=O, OH group attacks and etc to make cyclic acetal

aldehyde or ketone with 2 OH groups on the same molecule; intramolecular acetal formation

R-NH₂

cat acetic acid

aldehyde or ketone; NR double bond in place of the C=O

RNR

cat acetic acid

aldehyde or ketone; NR replaces C=O and double bond is down there

H₂N-R

NaCNBH₃

cat acetic acid

aldehyde or ketone; reduces C=O to HN-R

cat acetic acid

HO-NH₂

aldehyde or ketone; reduces C=O to C=NOH

H₂N-NH₂

KOH

heat

aldehyde or ketone; reduces C=O to 2 hydrogens

LDA, -78C

aldehyde or ketone; forms kinetic enolate (alkene and -O) on less sub side

thermo

aldehyde or ketone; forms thermo enolate on more sub side

NaOH

H₂O

aldehyde or ketone; no heat so self aldol condensation where -OH attacks alpha H to make O- (if there is workup, it will become OH)

aldehyde or ketone; no heat but OH/C=O and another C=O are on the same molecule, then aldol condensation occurs to kick off OH to form an alkene

HCl

H₂O

aldehyde or ketone; aldol condensation

NaOMe

heat

aldehyde or ketone; if there are 2 in one molecule than it will be an intramolecular aldol condensation with 5/6 membered ring preferred

1. - Nuc

2. HA

ketone; lower temp, harder nuc (high, localized, more EN) will add the Nuc with the C=O to make OH and Nuc

ketone; higher temp, softer nuc (low, diffuse charge) will add the nuc 1,4 addition

1. R - CuLi - R

2. H₃O+

ketone; 1,4 addition

NaOET

EtOH

ketones; 1 molecule that has two ketones plus 1 ketone molecule WITH ALKENE where -OET makes attacking alkene of molecule 1 to attack the alkene of molecule 2 and the O- goes down to attack alkene to attack H (michael addition)

NaOET

EtOH

heat

ketones; if heat then it is robinson annulation to make a 6 membered ring where molecule 1 with the two ketones have H taken away and the alkene that forms will attack the alkene of molecule 2. then undergo aldol condesation

CrO₃

H₂SO₄, H₂O

alcohols; if 1° then carboxylic acid, if 2° then ketone, if 3° nothing happens

aldehydes; turns into carboxylic acid

1. (COCl)₂

2. NEt₃

alcohols; if 1° then aldehyde, if 2° then ketone, and if 3° nothing happens

DMP

alcohols; if 1° then aldehyde, if 2° then ketone, and if 3° nothing happens

TMSCl / TBSCl

alcohols; protecting groups that turn OH to OTMS, and to remove, use TBAF

OH - - - OH

cat HCl

ketones and aldehydes; turns C=O into an acetal and use cat HCl and water to remove protecting group

1. Mg

2. CO₂

3. H₃O+

leaving group; is turned into a carboxylic acid

- Nuc

C=O with a Lg; -Nuc attacks C=O and the O- kicks off the Lg

H-Nuc

C=O with a Lg; NucH attacks C=O, remove the H on Nuc, and the O- kicks off the LG

NaOH

esters; -OH added to C=O, and if no work up step, it will be O- (soap)

HOR’

NaOR

esters: ester to another ester by kicking off initial ester

H₂O

acid catalyst

esters; OR’ of ester turns into OH with byproduct of HOR’

HOR’

acid catalyst

carboxylic acid; OH turns into OR’ with a byproduct of water

DCC

R-N=C=N-R

carboxylic acid; OH turns into NH_xR

amide with H₂O and strong acid

amides; NR_x turns into OH

amide with H₂O with NaOH and heat

amides; NR_x turns into O- (if no workup)

O=CLg with LiAlH₄ and H₃O+

C=O; it reduces to OH and H

O=CLg with NaBH₄

C=O; cannot reduce esters, amides, or carboxylic acids

1. DIBAL-H

2. H₃O+

esters; reduces esters to aldehydes

1. RMgBr (2 equiv)

2. H₃O+

O=CLg; reduces to OH and two R groups

O=C-NR₂; N group is replaced with R of MgBr

1. NaOEt

2. H₃O+

esters; H gets taken and attacks another of itself and remember the alpha proton at the end of else claisen cannot work

2 esters in one molecule → 5/6 membered rings intramolecular

heat

carboxylic acid with another C=O in the same molecule; the carboxylic goes off to form CO₂

Cl₂

FeCl₃

aromatic rings; Cl adds to the ring

HNO₃

H₂SO₄

aromatic rings; NO₂ adds to the ring

SO₃

H₂SO₄

aromatic rings; SO₃H adds to the ring

AlCl₃

makes Cl a good electrophile → aromatic ring attacks to add it

review diels-alder