Aldehyde and Ketone Reactions

PCC, CH₂Cl₂

(1^o alc)

Aldehyde

PCC, CH₂Cl₂

(2^o alc)

Ketone

1) O₃

2) DMS

(alkene)

2 carbonyl products (aldehydes or ketones)

(splits alkene)

HgSO₄, H₂SO₄, H₂O

(alkyne)

alkyne to Markovnikov Ketone

(changes alkyne to alkene w/ markovnikov, trans -OH and -H then reduced to ketone)

1) BH₃, THF

2) H₂O₂, NaOH

(alkyne)

Alkyne to Anti-Markovnikov Aldehyde

(changes alkyne to alkene w/ anti-markovnikov, cis -OH and -H then reduced to ketone)

H₂O, TsOH

Splits into two -OH groups

(Hydrate)

R-OH (2 equiv.), TsOH (cat), -H₂O

Splits into 2 -OR groups

(Acetal - Reversible w/ TsOH (cat), H₂O)

HO-R-OH (1 equiv), TsOH (cat), -H₂O

Splits to connect O-R-O group

(Cyclic Acetal - Reversible w/ TsOH (cat), H₂O)

H₂N-R, TsOH (cat), -H₂O

DB with O replace with DB with N-R group

(Imine - Reversible w/ TsOH (cat), H₂O)

R-NH-R, TsOH (cat), -H₂O

Moves DB to neighboring C (N cant accomodate DB), adds NR_{2 group}

(Enamine - Reversible w/ TsOH (cat), H₂O)

HS-R-SH, TsOH (cat), -H₂O

Splits to connect S-R-S group

(Cyclic Thioacetal - irreversible)

NaBH₄, MeOH

or

1) LiAlH₄

2) H₃O⁺

Aldehyde → 1^o alc

Ketone → 2^o alc (racemic)

1) R-MgBr

2) H₃O⁺

^or

1) R-Li

2) H₃O⁺

Aldehyde → 2^o alc (racemic)

Ketone → 3^o alc (racemic)

HCN, KCN

or

KCN, HCl

splits into -OH and -CN groups

(aldehyde has -H, ketone has -R)

(Cyanohydrin formation)

Zn(Hg), HCl, Δ

or

1) H₂NNH₂, TsOH (cat), -H₂O

2) KOH, H₂O

or

1) HS-R-SH, TsOH (cat), -H₂O

2) Raney Ni, H₂

Reduces to alkane