OChem reactions by functional group created

Ether Formation:

1) a —1. H2SO4, ∆ >140°C—> b

2) a —1. TosCl, pyridine, 2. R’—O^- —> c

3) a —1. Na (metal) —> b —2. 1° R—X —> d

ether formation:

1a: 1° OH — ? —> R—O—R (symmetrical)

2a: OH —?— > OTs —?—> R—O—R’ (unsymmetrical)

3a: OH —?—> O^- —?—> R—O—R’ (unsymmetrical, SN2 [no cation])

Chain Lengthening

1) a —1. NaNH2, RBr—> b

2) a —1. Mg, ether 2. (R=O) or (R—O) 3. H30+ —> b

chain lengthening

1a: Alkyne —?—> Alkyne—R

2a: R—X —1.?, 2?, 3? —> R—2.

Alkene Formation

1) a — Na/NH3—> b

2) a — H2, lindlar’s—> b

3) a — H2SO4, ∆ > 180°C —> b

4) a — NBS, hv —> b

alkene formation

1a: Alkyne —?—> trans alkene (anti-addition)

2a: Alkyne —?—> cis alkene (syn-addition)

3a: 3°, 2° OH —?—> Alkene (zaitsev product)

4a: Alkene —?—> Allylic Halide (allylic addition)

Alkyne formation

1) a — base —> b —1. NaNH2, 150°C —> c

2) a — base —> b —1. KOH, 200°C —> c

alkyne formation

1a: Alkane —?—> alkene —?—> Terminal Alkyne

2a: Alkane —?—> alkene —?—> Internal Alkyne

Alcohol Formation

1) a —H2, Raney Ni —> b

2) a —1. H20 2. H+ —> b

3) a —1. Hg(OAc)2, H20 2. NaBH4 —> b

4) a —1. BH3 · THF 2. H202, ^-OH —> b

5) a —1. X₂ 2. H2O —> b

6) a —1. OsO4, H2O2 or 1. KMnO4/OH, cold, dilute —> b

7) a —1. MCPBA, DCM 2. H+, H2O —> b

8) a —1. R—MgX, ether 2. C=O 3. H3O+ —> b

9) a —1. NaBH4, ether 2. H2O —> b

10) a —LiAlH4, H3O+ —> b

11) a —1. NaNH2 2.C=O 3. H30+ —> b

alcohol formation

1a: C=O —?—> OH (All sensitive groups have H added)

2a: C=C —?—> OH (Markonikov)

3a: C=C —?—> OH (Markonikov, anti-addition)

4a: C=C —?—> OH (Anti-Markonikov, syn-addition)

5a: C=C —?—> XC—COH (Markonikov, anti-addition)

6a: C=C —? or ?—> HOC—COH (syn-addition)

7a: C=C —1.? 2?—> HOC—COH (anti-addition)

8a: C=O —?—> OH

9a: C=O —?—> OH (only works for ketones and aldehydes)

10a: C=O —?—> OH (Ketone/Aldehyde —> 2°, 3°. Ester, C.A. —> 1°)

11a: Alkyne —1.? 2.? 3.? —> OH

Alkane Formation

1) a — H2, Pd —> b

2) a — LiAlH4 —> b

alkane formation

1a: Alkene —?—> Alkane (Syn-addition)

2a: C—OTs —?—> CH

Ring Formation

1) a — CH2I2, Zn(Cu) —> b

2) a — MCPBA, DCM —> b

3) a — Na (metal) —> b

ring formation

1a: C=C —?—> Carbon ring

2a: C=C —?—> Epoxide ring

3a: trans OH, X alkene —?—> Epoxide ring

Halo Alkene Formation

1) a — HX —> b

2) a — HBr/ROOR —> b

3) a — X₂—> b

4) a —NBS, hv—> b

halo alkene formation

1a: alkyne —?—> XC—CH (Markonikov)

2a: alkyne —?—> HC—CX (Anti-markonikov)

3a: alkyne —?—> XC—CX (Anti-addition more likely)

4a: Alkene —?—> C=C-Br (Allylic Bromine)

Halo Alkane Formation

1) a — 2X₂—> b

2) a — HBr/ROOR —> b

3) a — HX —> b

4) a — X₂ —> b

5) a —HBr or HCl, ZnCl2—> b

6) a —PBr3 or PCl3 or P/I2 —> b

7) a —SOCl2 or SOCl2, pyridine —> b

halo alkane formation

1a: Alkyne —?—> 2XC—CX2

2a: C=C —?—> BrC—CH (Anti-markonikov)

3a: C=C —?—> HC—CX (Markonikov)

4a: C=C —?—> XC—CX (Anti-addition. cis—> racemic, trans —> meso)

5a: OH —2?—> C—X (3°, 2° —> SN1 (cation), 1° —> SN2 (flips stereochemistry)

6a: OH —3?—> C—X (1°, 2° —> SN2) gives good yield

7a: OH —?—> C—X (w/pyridine, flips stereochemistry)

Ketone Formation

1) a —1. O3 2. (CH3)2 S —> b

2) a —1. Hg(SO4), H+, H2O 2. H+ —> b

3) a —1. KMnO4, H20, pH=7 2. -2H20 —> b

4) a — Na2Cr2O7, H2SO4 or PCC, DCM or DMP or NaOCl, H2O, or Swern —> b

5) a — 1. OsO4, H2O2 2. HIO4 —> b

6) a —1. R—MgX, ether, 2. H3O+ 3. Na2Cr2O7, H2SO4 —> b

ketone formation

1a: C=C —?—> C=O O=C

2a: Alkyne —1.? 2.? —> Ketone

3a: Alkyne 1.? 2.? —> Diketone

4a: 2° OH —5?—> Ketone

5a: C=C —1.? 2.? —> C=O O=C

6a: CHO —?—> 2° OH —?—> Ketone

Carboxylic Acid Formation

1) a — KMnO4, ∆, Conc. —> b

2) a — KMnO4, H2O, ∆, pH≤1 or pH>7—>

3) a — O3, H2O —> b

4) a — Na2Cr2O7, H2SO4 —> b

carboxylic acid formation

1a: C=C —?—> 2 C.A.

2a: Alkyne —?—> C.A

3a: Alkyne —?—> C.A.

4a: 1° OH —?—> C.A.

Aldehyde Formation

1) a —1. Sia2BH 2. H2O2, ^-OH —> b

2) a — PCC, DCM or DMP or Swern, or NaOCl, H2O —> b

aldehyde formation

1a: Alkyne —?—> aldehyde (Anti-markonikov)

2a: 1° OH —4?—> Aldehyde

Ester Formation

1) a —ROH, H+—> b

ester formation

1a: C.A. —?—> Ester