Acid/Base

Electrophile/Nucleophile

Neutralized Substance (frequently HOH)

A + :B → AB

Sn2

Alkane w/ Leaving Group (1°)

 to

Replaced Leaving Group

Nucleophile

   H                      H              H

C-C-L + :Nu →[ Nu-C-L ] → Nu-C-C + :L

   H                     CH              H 

Inversion

Sn1

Alkane w/ Leaving Group (2/3°)

to

Alkane w/ New Substituent (has E1 by-product)

Nu:

   C          C                    C 

C-C-L → C-C + + :Nu → C-C-Nu

   C           C                   C

Racemate

E2

Alkane w/ Leaving Group (1/2°)

to

Alkene

Nu:

      H                                  H              H

H-C-C-L + :Nu → [Nu--H--C==C--L] → C=C

      H                                  H              H

E1

Alkane w/ Leaving Group (3°)

to

Alkene

Nu:

      C            C                                     C 

H-C-C-L →  H-C-C+ + :Nu → [ Nu--H--C==C ] →

      C            C                                     C

    C

C=C

    C

Dehydrohalogenation

Alkyl Halide

to

Alkene

Nu:

By E2/1

Acid Catalysed Dehydration

Alcohol (3º>2º>1º)

to

Alkene

Strong Acid

H adds to -OH

Proceeds as E1/2

Double Elimination

Vicinal Dihalide

to

Alkyne

Nu: (2eq)

2 repeated E2 reactions

Rearrangement

1º/2º Cation

3º Cation

An entire subsituent moves over to the 1º/2º cation to make more stable

Replacement

Terminal Alkyne

to

Terminal Alkynide

NaNH₂, NH₃, Li...

R-CΞC-H → R-CΞC:

Hydrogenation

Alkene

to

Alkane

H₂, Pd/Ni

Double bond attacks H in H₂

Hydrogenation

Alkyne

Syn Alkene

 OR

Anti Alkene

Ni₂B, H₂

OR

Li, EtNH₂ (Radical)

Addition

Alkene

to

Alkyl Halide

HX

Double bond attacks H (adds to side w/ most H's), creates a Cation, X- attacks.

 REARRANGEMENT can happen.

Acid Catalysed Hydration

Alkene

to

Alcohol

1)HA

2) OH^-

Double bond attacks H on Acid, then Conj. Base attacks cation.  OH^- attacks C with sulfonate.

Acid Catalysed Hydration

Alkene

to

Alcohol (3º/2º)

SA, H₂O

Double bond attacks H on acid, forms cation.  H₂O attacks cation.  Conjugate base deprotonates the O⁺ formed.

Oxymercuration/Demercuration

Alkene

to 

Alcohol (no rearrangement)

Hg(COOCH₃)₂ , THF (becomes Cation), H₂O

Double bond attacks Hg, forms bond from both C's.  Hydrogenation occurs. 

NaBH₄, OH^-

H^- attacks C w/ Hg

Hydroboration

Alkene

to

Alkyl Borane

BH₃

Double bond attacks B, kicks out an H

(occurs for each H)

Oxidation and Hydrolysis

Alkylborane

to

Alcohol

HOO^-, NaOH

Peroxide Ion attacks B, R attacks 1^st O, forms ether.  Repeats 3 times.

OH^- attacks B, kicks out ^-O-R, which attacks H on BOROH. 

Addition

Alkene

to

Vicinal Dihalide

Cl₂, CCl₄

C=C forms ring with a Cl, Cl^- attacks from other side

TRANS

Addition

Alkene

to

Halohydrin

X₂, H₂O

C=C forms ring with X, H₂O goes through Hydration

Carbene Formation

Diazomethane (:CH₂-NΞN:)

to

Carbene

hν

N-C bond breaks and

:CH₂ forms

Cyclopropane formation

Alkene

to

Cyclopropane

Carbene

Cyclic donation from double bond to carbene and vice versa.

Oxidation

Alkene

to

Diol (Syn)

1) OsO₄, Pyradine 2)NaSO₃/H₂O

OR

KMnO₄, OH^-, H₂O

Double Bond attacks an O, an O attacks the other Carbon, and the H's attack at O bonds.

Oxidative Cleavage

Alkene (alkyne)

to

Carboxylic Acid, CO₂, or Ketone (carboxylic acid)

1) KMnO₄, OH^-, H₂O, heat 2)H₃O⁺

Breaks double bond, adds a =O.

Oxonolysis

Alkene

1) O₃, CH₂Cl₂ 2) Zn, HOAc

Aldehyde/Ketone

Forms C-C Ring

   O-O-O

Which changes to a C-O-C Ring

                     O  O

Which breaks apart w/ Zn, HOAc

Addition

Alkyne

to

Dihaloalkene (trans)

Tetrahaloalkane

X₂, CCl₄

Adds 1/2 times depending on eq

(like addition to Alkene).

Addition

Alkyne

to

Haloalkene

HX (for Markovnikov)

HX and ROOR (for Anti-Markovnikov)

Addition

Haloalkene

to

Geminal Dihalide

HX

Adds Markovnikov, so adds X to C with other X.

Radical

Alkane

to

Alkyl Halide

X₂, Light

Cl· abstracts the H, leaving a radical.  Cl· attacks the radical.

Anti-Markovnikovian Addition

Alkene

to

Alkyl Halide

HX, light, ROOR

RO· abstracts H from HX, X· attacks double bond, the radical C abstract and H from HX.

Substitution

Alcohol

to

Alkyl Halide

HX, PBr₃, SOCl₂ and pyradine

OH attacks either P or H, making a good leaving group.  X^- will then attack the C.

Intermolecular Dehydration

1º Alcohol

to

Ether

HA

R-OH → R-OH₂ → [ROH--R--OH₂] → ROR → ROR

                                        H

Williamson Synthesis

Alcohols

to

Ether

K or NaH and R'-L

R-OH → R-ONa/K → R-O-R' (Na/K⁺ and L^-)

Alkoxymercuration/Demercuration

Alkene

to

Ether

1) Hg(OOCCF₃)₂, HO-R'

2) NaBH₂, OH^-

Protecting Groups

Alcohol

to

Protected Ether

H₂SO₄, C=C(CH₃)₂

 OR

ClSi(CH₃)₂CH₃, Imidiazole, DMF

(Bu₄NF, THF to remove)

Use to get a base to attack a C rather than an H

Cleavage

Ether

to

Alkyl Halide and Alcohol

H-X

H adds to O, stablest cation forms (or X attacks-Mark)

     H 

  R-O-R' → R-OH + R'⁺ or R'X

Formation of Epoxides

Alkene

to

Epoxide

Peroxyacid

Forms cyclic bond with OH from ROOH, also forms a carboxylic acid

Acid Catalysed Ring Opening

Epoxide

to

Akyl ____

Water or other Weak Acid

O attacks H from Acid, acid attacks C and OH breaks off to form an Alkyl whatever.

Base Catalysed Ring Opening

Epoxide

to

Alkyl______

Strong Base and NH₄Cl

Base attacks the C, O breaks off, attacks a Hydrogen.

Reduction by Hydride Transfer

Carboxyl Group

to

Alcohol

1) LiAlH₄, Et₂O 2) H₂SO₄/H₂O

or

BH₄, H₂O

Donates an H, O^- attacks an H (or pushes out an OH^-)

Oxidation

Alcohol

to

Aldehyde (1°), Carboxylic Acid (1°), or Ketone

PCC, CH₂Cl₂

or

KMnO₄, OH^-, H₂O, heat, H₃O⁺

or

CrO₃ (HCrO₄, Acetone), H₂O (JONES REAGENT)

Organometal Formation

Alkyl Halide

to

Organometal

Mg or Li (Et₂O, THF)

Replaces X

Acid/Base

(What can go WRONG)

Carboxyl group with an acidic H

to

Alkane

Organometallic attacks the H rather than the C with the =O

(Works with -OH, and CΞCH notably)

Grignard/Lithium Rxn

Carboxyl Group

to

Alcohol

Grignard/Organolithium Reagent or C≡C:, H₃O⁺

R group on Organometallic attacks C with =O.

 Also works in Epoxides with C-O

Esters will act as a leaving group

Corey-Posner, Whiteside-House Synthesis

Alkyl Halide

to

Dialkyl cuprate

Li in Et₂O and CuI

Li replaces X, Cu takes place of Li to get CuLi compound with 2 alkyl groups

Corey-Posner Whiteside-House Synthesis

(part deux)

Alkyl Halide

to

Alkane

Dialkyl Cuprate

Alkyl Group takes place of X

Allylic Substitution

Alkene with ≥1 branch

to

Halo-alkene

X₂, Heat

also: NBS, hv, CCl₄

X· Forms, abstracting an H and leaving a radical on an allylic carbon.  Through RESONANCE, many different placements of the X occur.

Diels-Alder Reaction

Diene (best if with e^- donating group)

to

Six-Membered Ring

Alkene with e^- withdrawing group (Electron Acceptor)

Resonance makes the donor/acceptor possible, number carbons along double bonds 1-4 and 5-6 to show bonds of ring.

***IN=UP, OUT=DOWN***