Compendium of Organic Synthetic Methods, Volume 9. Michael B.

Smith
Copyright 2001 by John Wiley & Sons, Inc.
ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)

48 Compendium of Organic Synthetic Methods, Vol9 Section 48

CHAPTER 4
PREPARATION OF ALDEHYDES

SECTION 46: ALDEHYDES FROM ALKYNES

NO ADDITIONAL EXAMPLFS

SECTION 47: ALDEHYDES FROM ACID DERIVATIVES

Ph a
Cha, J.S.; &own.
Cl
HL
AlH(O&Bu)3 , diglyme-THF

-78OC
J. Org. Chem., 1993, 58, 4732
t
Ph a H
81%

quant.
Maeda, H.; Maki, T.; mri. fL Tetrahedron Lett., 1995, 36, 2247

1.2 eq. piperidine , THF , rt

2.2 eq. NaEtzAlH2, rt , lh

74%
Yoon. N.M,; Choi, K.I.; Gyoung, Y.S.; Jun, W.S. Synth. Commun., 1993, 23, 1775

SECTION 48: ALDEHYDES FROM ALCOHOLS AND THIOLS

Mn02, Bentonite CHO

microwave
60%
OMe
Martinez, L.A.; Garcfa, 0.; Delgado, F.; Alvarez. C,; Patifio, R. Tetrahedron L&t., 1993, 34,
5293
Section 49 Aldehydes from Alkynes 49

TCM (trichloromelamine)
CH2C12, rt ,2Oh
PhCHzOH PhCHO 83%

also oxidizes 2 alcohols to ketones

Kondo. S ,; Ohira, M.; Kawasoe, S .; Kunisada, H.; Yuki, Y. J. Org. Chem., 1993, 58, 5003

5% CpRu(PPh&Cl , 10% (C2H$#HPF6

PhMOH * PhOH
8h
90%
mt. R.m; Kulawiec, R.J. J. Am. Chem. Sot., 1993, 115, 2027

hydrous zirconium (IV) oxide

Me$iCl , PhCHO , xylene
t
W-h~OH C5H1 IBCHo

67%
Kuno. H.; Shibagaki, M.; Yakahashi, K.; Matsushita, H. Bull. Chem. Sot. Jpn., 1993, 66,
1699

#OH CHO

.
dI \0
DMSO , rt

also for the preparation of ketones and 1,2-diketones

d
I
0
\
88%

WM.; . Santagostino, M. Tetrahedron Lett., 1994, 35, 8019

Montmorillonite K-10, pentane

)c PhCHO
PhloH KzFe04,3h 63%
Delaude, L.; Laszlo, P,; Lehance, P. Tetrahedron Lett., 1995, 36, 8505

PhCH20H PDC/Adogen 464 98%

t PhCHO
Mohand, S.A.; Muzart. J, Synth. Commun., 1995, 2.5, 2373

SECTION 49: ALDEHYDES FROM ALKYNES

Conjugate reductions and Michael Alkylations of conjugated aldehydes are listed

in Section 74 (Alkyls from Alkenes).
50 Compendium of Organic Synthetic Methods, Vol9 Section 51

Phillips, O.A.; Eby, P.; Maiti. S.N,Synth. Commun., 1995, 25, 87

1. Me@, KOH , Hfl

PhCHO w PhCH2CH0
2. SiO2
Lemini, C.; Ordoflez, M.; Perez-Flores, J.; Cruz-Almanza. Synth. Commun., 1995, 25, 2695

1.

PhCHO 2. H20 a pf-d-dCHo

3. N&O3 85%
Schummer. D,; Hofle, G. Tetrahedron, 1995, 51, 11219

Related Methods: Aldehydes from Ketones (Section 57)

Ketones from Ketones (Section 177)
Also via: AIkenyl aldehydes (Section 341)
SECTION 50: ALDEHYDES FROM ALKYLS, METHYLENES
AND ARYLS

72x72%
VeteIino, M.G.; (be. J.W. Tetrahedron Let?., 1994, 35, 219

Hc-c=j-C,, *r03 cAN g50c * H+-CHO

70%
Ganin, E.; Amer. I, Synth. Commun., 1995, 25, 3149

SECTION 51: ALDEHYDES FROM AMIDES

NO ADDITIONAL EXAMPLES
Section 53 Aldehydes from Esters 51

SECTION 52: ALDEHYDES FROM AMINES

1. BuLi Bu
2. H30+
98 x 70%
; Carter, D.S.; Dubree, H.J.P. Tetrahedron Lett., 1993, 34, 3255

Related Methods: Ketones from Amines (Section 172)

SECTION 53: ALDEHYDES FROM ESTERS

c6 13 C 13
Bu$nH, PhH
SPh H 93%
PhS 0.4% Pd(PPh3)4 PhS 199 (E.-Z)
h * %f
0 0
Kuniyasu, H.; Ogawa, A.; Sonoda N, Tetrahedron Lett., 1993, 34, 2491

C02Me
1.5% Cp2TiClfiuLi OH
polymethyl-hydrosiloxane
THF
2. workup 65%
Barr, K.J.; Berk, S.C.; Buchwald. S.L,J. Org. Chem., 1994, 59, 4323

mC02Et NaAlH(NEt2)3 , THF ,6h -CHO

w

65%
Cha. J.S ; Kim, J.M.; Jeoung, M.K.; Kwon, 0.0.; Kim, E.J. Org. Prep. Proceed. Int., 1995,
27,95

Ca(BH& , 1,5-cod, THF

CllH23C02Me * CllH23CH20H 95%
Narasimhan, S.; Prasad, K.G.; Madhavan, S. Synth. Commun., 1995, 25, 1689

1. PhMezSiLi , THF, -1lOOC

MeC02Me 2, MeCHO 70x74%
2. CrO3, DMSO , rt
Fleming. I,; Ghosh, U. J. Chem. Sot., Perkin Trans. I., 1994, 257
52 Compendium of Organic Synthetic Methods, Vol9 Section 55

REVIEW:
Asymmetric Reductions of C-N Double Bonds. A Review, Zhu, Q.-C.; Hutchins. R.Q, Org.
Prep. Proceed. Int., 1994, 26, 193

SECTION 54: ALDEHYDES FROM ETHERS, EPOXIDES AND

THIOETHERS

LiCLO4 , ether
0
rt ,6h * cpCHO
w 60%
Palani, N.; Balasubramanian. K.K, Tetrahedron Lett., 1995, 36,9527

Bu

..
MABR , CH2C12, -2OOC (0 100) 73%
.
SbF3 , PhH ,25OC (85 15) 62%
Maruoka, K.; Murase, N.; Bureau, R.; Ooi, T.; Yamamoto, H, Tetrahedron, 1994, 50, 3663

LiTMP ,THF , 20C

) CloH21~cH0
ClOH2lJ

83%
Yanagisawa, A.; Yasue, K.; Yamamoto. H, J. Chem. Sot. Chem. Commun., 1994, 2103

Related Methods: Ketones from Ethers and Epoxides (Section 174)

SECTION 55: ALDEHYDES FROM HALIDES AND SULFONATES

1. iPr$i-SH/KH
2. TBAF, THF
H
*
PB 3. Hz0 P
88~73%
Miranda, E.I.; Diaz, M.J.; Rosado, I.; Sode qust. J.A, Tetrahedron L&t., 1994, 35, 3221
Rane, A.M.; Miranda, E.I.; Soderauist, J,A: Titrahedron Lett., 1994, 35, 3225

30 atm CO , SiH(SiMe$y , PhH

CSH 1743r e W174HO + octane (16%)
AIBN , reflux 80%
WI.; Hasegawa, M.; Kurihara, A.; Ogawa, A.; Tsunoi, S.; Sonoda N,Synlett, 1993, 143
Section 58 Aldehydes from Nitriles 53

(f-o/ 0-d
02
- Br 1. PhLi , THF , -78OC 02
- CHO
t
vI 2.
C l+CHO
I
v 84%

Me Me
Hardcastle, I.R.; C)Yilvle. P,; Ward, E.L.M. Tetrahedron Lett., 1994, 35, 1747

OMs OH
MeMgBr , THF

Cossv. J,; Ranaivosata, J.-L.; Bellosta, V.; Wietzke, R. Synth. Commun., 1995, 25, 3109

CHBrz CHO
NaOAc , CaCO3,7h
TBAB , H20, reflux
\
64%
I
b /
CHBr2 CHO
m. S,; Liu, G.-B.; Sawada, T.; Tori-i, A.; Tashiro, M. J. Chem. Res. (S), 1995, 410

SECTION 56: ALDEHYDES FROM HYDRIDES

NO ADDITIONAL EXAMPLES

SECTION 57: ALDEHYDES FROM KETONES

1. TMSC(Li)Nz , THF , iPr2NH CHO

-78OC + reflux
Pha *Phd
2. Hz0
72%
. . . . T,
Miwa, K.; -T.. Synlett, 1994, 109

SECTION 58: ALDEHYDES FROM NITRILES

NaAIH(NEt& , THF ,25OC

PhCN PhCHO 97%
Cha. J&; Jeoung, M.K.; Kim, J.M.; Kwon, 0.0.; Lee, J.C. Org. Prep. Proceed. Int., 1994, 26,
583
54 Compendium of Organic Synthetic Methods, Vol9 Section 59

SECTION 59: ALDEHYDES FROM ALKENES

Rh(acac)(CO)2, H&O
100 atm , 60C, PhH ,42h

(90 .. 10)
> 99% conversion
Higashizima, T.; Sakai, N.; Nozaki, K.; Takava, H, Tetrahedron Lett., 1994, 35, 2023

4 eq. PhSH , EtflOTs , MeCN

Ph
* PhS-CHO 77%
e (0.05 F mol-)
Yoshida. J,; Nakatani, S.; Isoe, S. J. Org. Chem., 1993, 58, 4855

S.-Q, Jung, K.-Y.; Chung, J.-U.; Namkoong, E.-Y.; Kim, T.-H. J. Org. Chem., 1995,
60,4678

CHO
H
n

8 8
OHC
Hz, CO (1600 psi)
t /
\
\ +
/ 1
carbohydrate-OPAr2

/ \
/ 1
53% conversion 51%ee(96 : 4
RajanBabu, T.V.; Ayers. T.A, Tetrahedron Lett., 1994, 35,4295

CO,&
+
Ph [Rh(cod)IOAc)]2 Ph CHO
(96 .. 4) 94%
D~M.P.; Shanklin, M.S.; Zlokazov, M.V. Synlett, 1994, 615
Section 60A Protection of Aldehydes 55

Rh(acac)(CO)rBINAPHOS
82% ee
Hz/CO (100 atm) , PhH , 60C ,62h* A CHO
Sakai, N.; Nozaki, K.; ma. I-l. J. Chem. Sot. Chem. Commun., 1994, 395

CO, Hz, 5% Rh(cod)L BF4

+ phICHo
PhH, 55OC CHO
L = bis phosphine .
(3 .5 1)
Ghan. A.S.C,; Pai, C.-C.; YanG T.-K; Chen, S.-M. J. Chem. So;. Chem. Commun., 1995,
2031

Related Methods: Ketones from Alkenes (Section 179)

SECTION 60: ALDEHYDES FROM MISCELLANEOUS

COMPOUNDS

MeCN , CuC12e2 Hz0

Ph * P
H H
Singh, L.; m. R& Synth. Commun., 1993, 23, 3139

H
Ph I TMSCl , NaN02, Ccl4
NN NH2 95%
L -N -) PhCHO
Aliquat 336
K
0
Khan. Rx; Mathur, R.K.; Ghosh, A.C. J. Chem. Res. (S), 1995, 506

SECTION 60A: PROTECTION OF ALDEHYDES

-Q
AC
A1203 (neutral) , microwave
P w PtiCHO
CH2C12, rt 98%
-0Ac
Vu.; Chatterjee, AK.; Varma, M. Tetrahedron Lett., 1993, 34, 3207

Ph 2 eq. AgN02, 12, THF

96%
rt, 30min
Ph Ph

also works with dithianes also for protected ketones

Nishide, K.; Yokota, K.; Nakamura, D.; Sumiya, T.; &de. M.; Ueda, M.; Fuji, K. Tetrahedron
Lett., 1993, 34, 3425
56 Compendium of Organic Synthetic Methods, Vo19 Section 59

t-BuOK,THF,rt,2Omin
P t P+CHO 95%

Ox+
I(u. Y.-Y.; Patel, R.; Sawick, D. Tetrahedron Lett., 1993, 34, 8037

SPh DDQ , H20, MeOH

Ph
T SPh hv (h > 350 nm)
) Ph-CHO

95%
Mathew, L.; sankararaman. .I. Org. Chem., 1993, 58, 7576

p-TsOH , MgS04, PhH

PheCHO
ethylene glycol , reflux ,4.5h * phTJ
97%
Lu, T.-J,; Yang, J.-F.; Sheu, L.-J. J. Org. Chem., 1995, 60, 2931

HS SH , C&Q2
CHO
(t CoBr$Si02,3 min

also with ketones 99%

WY. H.K. Tetrahedron z&t., 1994, 35, 5717

2 EtSH , HY zeolite , CHg12 SEt

-CHO w I
35OC MSEt
ketones can also be used
92%
Kumar.; Reddy, R.S.; Singh, A.P.; Pandley, B. Synthesis, 1993, 67

ethylene glycol , TsOH

ph-cHo
microwave, 2 min

ketones can also be used

Monhaddam. F.M; Sharifi, A. Synth. Commun., 1995,25, 2457

Section 60A Protection of Aldehydes 57

MoOz(acac)z , MeCN ,4h

PhCHO

97%
Kantam. b&; Swapna, V.; Santhi, P.L. Synth. Commun., 1995, 25, 2529

1,2+%hanediol, cat. CAN

PhCHO * Ph
CHC13 , rt , overnight 85%

ketones can also be used

Mandal, PK.; Boy. S.C, Tetrahedron, 1995, 51, 7823