USEFUL SYNTHETIC PREPARATIONS

Annual Reports in Organic Synthesis-1977

VI.A.1-1

N. Ishikawa and S. Sasaki, Chem. Lett., 483 (1977). 0

0

CF 3 CF 2 CF=0

II

R-C-F

R-C-OH R = Et, i-Pr, Ph

VI.A.1-2 (1977).

a,85%

Y. Nagai et al., J. Chem. S o c , Chem. Commun., 808

Jω-

(Me 3 Si) 2 0

CCI.

0

,£H-

ci

74-84%

R = Cl, CCI,

VI.A.1-3 H. Schick, S. Schwartz, and U. Eberhardt, J. Prakt. Chem., 319, 213 (1977).

< *

A V

NaOH

0 R = Me, Et

>90%

R' == a l l y l , CH2COOH

04*

Copyright© 1978 by Academic Press, Inc. All rights of reproduction in any form reserved. ISBN 0-12-040808-2

ORGANIC SYNTHESIS-1977

VI.A.1-4 kov, B.ull.

V. N. O d i n o k o v , L. P. Z h e m a i d u k , and G. A. A k a d . USSR Chem., 2 5 , 1790 ( 1 9 7 7 ) .

Tolsti-

^COOH

1. 0 3 , e t h e r


)

2. H 2 , L i n d l a r

80-99%

VI.A.1-5 9 £ , 4405

JC

B. M. T r o s t and G. S. M a s s i o t , J . Am. Chem. (1977). OAc 1.

PhSSPh

PhS

H 2 0 2 , NaOH

HOOC' y

2.

Pb(0Ac);

H00C>

\S

55-99%

VI.A.1-6

65-99%

F. M. Häuser and R. Rhee, S y n t h e s i s , 245

CH„ COOH

Soc,

1.

LDA, THF

2.

(Me0) 2 C0

(1977).

COOH COOH

85-90%

R = H, OMe

342

USEFUL SYNTHETIC PREPARATIONS D.H.R. Barton and S. C. Narang, J . Chem. S o c , VI.A.2-1 Perkin I , 1114 (1977). 1. N 2 0 4 — >2. Zn, AcOH

R-NHo

R-OH

R = n-octyl, cycloalkyl

VI.A.2-2 (1977).

^30-80%

K. Smith e t aJL_, J . Chem. S o c , Perkin I , 1172

R'

R

3

B

+

\S-> L1C > X S-^

?'

2. HgCl 2 3

·

Na0H

>

R H

9°9 ά

ά

R = n-alkyl, cycloalkyl

| i " I R

0 H

^80-90%

R'= H, n-Pr

VI.A.2-3 K. Isagawa, K. Tatsumi, and Y. Otsuji, Chem. Lett., 1117 (1977). 1. L i A l H 4 , C p 2 T i ( A l H 3 ) 2 2.

Oxidation

R-CH=CH2

*>

R = Ph, n - a l k y l , cyclohexenyl

RCH2CH20H 34-86%

343

ORGANIC SYNTHESIS-1977 VI.A.2-4 H. C. Brown and N. R a v i n d r i r a n , J . Org. Chem., 42_, 2533 (1977). —

1. Hc9BCl-SMeά9

ί

or Hά9BC1.0Et9 2. H 9 0 9 , NaOH

CHω90H | CH. / '2

·

ω

R

R = Ph, simple alkyl

VI.A.2-5 (1977).

generally >99%

H. C. Brown and S. C. Kim, J. Org. Chem., 42_, 1482 — 1. LiEt3BH

PhCH=CH2

2. CHoSOoH '3^3' 3. NaOH, H 2 0 2

PhCHCH3 y

OH 90%

PhCH=CHCH0

same conditions

y

PhCHCH2CH2 OH

OH

80% VI.A.2-6 H. C. Brown and N. M. Yoon, Israel J. Chem., 15, 12 (1977). — OH Diisopinocampheylborane / * \ x ^

344

USEFUL SYNTHETIC PREPARATIONS VI.A.2-7 T. Cohen, A. G. D i e t z , J r . , J . O r q . Chem., 4 2 , 2053 ( 1 9 7 7 ) .

© Me

È

and J . R.

Cu 2 0

N 2 HS0 4

Cu2+,

Miser,

OH

Me

H20

93%

VI.A.2-8 N. J . L e w i s , S. Y. Gabhe, and M. R. De La M a t e r , J . O r q . Chem., 4 2 , 1479 ( 1 9 7 7 ) .

1.

Br

Mg, THF

OH

y

2.

MoOPH

R

(MoO r -Py-HMPA) R = H, OMe, E t ,

67-89%

benzo

VI.A.2-9 G. Z w e i f e l , S. J . B a c k l u n d , and T . Chem. S o c , 9 ^ , 5194 ( 1 9 7 7 ) .

1.

h v , 6h CH 2 =CH(CH 3 )CH 2 CH

H2C=C-CH=CHB CH 0

L e u n g , J . Am.

2.

NaHB(s-Bu)3

69%

345

-O

OH

ORGANIC SYNTHESIS-1977 VI.A.3-1 V. P. Savel'yanov et. a l ^ , J . Org. Chem. (USSR), 1_3, — 604 (1977).

HC1, trinonyl borate

R-OH

R-Cl

130°, ZnCl 2 (on a column)

R = 1° alkyl

90-95%

VI.A.3-2 M. E. Jung and P. L. Ornstein, Tetrahedron Lett., 2659 (1977). Me 3 SiI

R-OH

R-I

Me^SiCl/pyr

R = 1°,2°,3° a l k y l ,

^70-100%

Me 3 SiI

cycloalkyl

VI.A.3-3 K. Isagawa, K. Tatsumi, and Y. Otsuyi, Chem. Lett., 1117 (1977). 1. L i A l H 4 , C p 2 T i ( A l H 3 ) 2 RCH=CH.

2.

Br 0 +

R = j i - a l k y l , Ph

RCH2CH2Br 50-87%

346

USEFUL SYNTHETIC PREPARATIONS I.A.3-4 R. M. Magid, 0. S. Fruchey, and W. L. Johnson, retrahedron L e t t . , 2999 (1977).

0 PPh 3 , C1 3 CCCC1 3

/==\

CH 3

/=\ CHQ CHpCl

CH 2 0H

98% same conditions

CH 2 =CH-CH-CH 3

y

CH2 = C H - C H - C H Q

OH

Cl 94%

VI.A.3-5

R. Mornet and L. Gouin, Synthesis, 786 (1977).

R1

R1 CICOOEt

R^

R2'

CH2N^

CH2C1

R

S

^80%

R1 = H, -C-alkyl R2 = 1°,2° a l k y l , Ph, H

VI.A.3-6 T. Kauffmann, H. Fischer, and A. Woltermann, Angew. Chem. Int. Ed., 16, 53 (1977).

R-X X = halogen R = 1° a l k y l

1. 2

*

PhJ\sCHJi Br

+

R-CH2Br

2 ^50-80% o v e r a l l 347

ORGANIC SYNTHESIS-1977

VI.A.3-7 T. Mukaiyama, S. Shoda, and Y. Watanabe, Chem. Lett., 383 (1977).

R I' \

1.

Et

BF 4

I©

^

Cl

R1

Et 3 N

Cl-C^R

C-OH 2.

H

Et 4 NCl

H

76-97%

R = alkyl, protected sugar

>90% inversion

VI.A.3-8

A. R. K a t r i t z k y ejt al_^, S y n t h e s i s , 634 (1977) Ph

Ph

0 Ö

>h À Ï

R-I

R-NH„ Ä

52-85%

R = alkyl, benzyl, pyridinyl

VI.A.3-9 P. Golitz and A. de Meijere, Angew. Chem. Int. Ed., 16, 854 (1977). R-NH„ R = n-alkyl,

CF 3 N0

R-N=N-CF.

cycloalkyl

348

hv

R-CF.

USEFUL SYNTHETIC PREPARATIONS

VI.A.3-10 L. M. Y a g u p o l ' s k i i , N. V. K o n d r a t e n k o , and V. I . Popov, J . O r g . Chem. (USSR), J 3 , 561 ( 1 9 7 7 ) .

PhSbF. PhCF-

Ph-CCl. o r Ph 2 SbF 3

up t o 91%

VI.A.3-11 T.-L. 676 ( 1 9 7 7 ) .

f

Ho, B . G . B .

CH

(OU 2'n || » L

CH

G u p t a , and G. A. O l a h ,

HX, HQOQ H909 HX,

/

L? —

^ *

phase-transfer cat.

n = 4,5,6

CHX

j ( v Vn (C

V

Synthesis,

-j

CHX

^75%

(X=C1)

^95%

(X=Br)

VI.A.3-12 Y. Echigo, Y. Watanabe, and T. Mukaiyama, Chem. Lett., 1013 (1977).

\

BF

Et

4 »C-C

Et 4 N©C10, Et 3 N

I I

CHpCl«

ci ci ^60-90%

alkyl, aryl, cyclic substituents

(syn functionalization)

349

ORGANIC SYNTHESIS-1977 VI.A.3-13 (1977).

M. Zupan and A. Pollak, J. Org. Chem., 42, 1559

PhCH=CHR

XeF2

Ph-CH-CH-R F

F

53-64%

R = Me, Ph, t-Bu

VI.A.3-14 S. A. Shackelford, R. R. McGuire, and J. L. Pflug, Tetrahedron Lett., 363 (1977). Simplified benchtop procedures for the use of XeF^ for alkene fluorination.

VI.A.3-15 (1977).

D.H.R. Barton, Pure and Appl. Chem., 49_, 1241 —

Review:

"The Invention of Reactions Useful for the Synthesis of Specifically Fluorinated Natural Products"

350

USEFUL SYNTHETIC PREPARATIONS VI.A.3-16 D. B e t h e l ! , K. McDonald, and K. S. Rao, T e t r a ­ hedron L e t t . , 1447 (1977).

Ph,CN9 6

C

H ? 0, KHF? /s c - — B u 4 N w C I O ^ , CH 2 C1 2

y

Ph?CHF c

^60%

J. Kagan et. aL_, J. Org. Chem., 42., 343 (1977).

VI.A.3-17

OH \

1. FeCl3, ether

>ÆË<

2. H20

^

/^

/ \

c l

55-78%

VI.A.3-18 F. M. Laskovics and E. M. Schulman, Tetrahedron L e t t . , 759 (1977).

\

R;

/ N "º

M

/

II C

1 . THF, -78°+0°

\

J

2. H 0 J

© U

3. NaHC03

o

||

R

cl

' R1

61-65% f o r cyclopentanone, cyclohexanone, cycloheptanone May give mixtures w i t h compounds which can give two enamine isomers.

351

ORGANIC SYNTHESIS-1977 VI.A.3-19

H. Nakai and M. Kurono, Chem. L e t t . , 995 (1977). Cl Ph-S-CH,

Ph-S-CH,

È

,1

,0

>

R3

^

Cl È

R1

►25°

0

Cl

H

R^R^R3 = a l k y l , a r y l , cyclic aq. NaHC03

Et 3 N

R1

0 R

Cl

2

^ — ^ R

Cl

R~

3

H >90%

>90%

(anti

addition)

VI.A.3-20 V. Reutrakul and W. Kanghae, Tetrahedron L e t t . , 1225 (1977). 0 Li 0 1.

Ph-S-CH-Cl, THF, -78°

2.

Ä, xylene

R-C-H R = n-alkyl

R-C-CH2C1 76-95%

352

USEFUL SYNTHETIC PREPARATIONS VI.A.3-21 S. H. Korzeniowski and G. W. Gokel, Tetrahedron L e t t . , 3519 (1977).

©

È

ÍÎÍ

BF,

I CH3I or I 2 CHC1

R

3

^50-90%

R = Me, OMe, Br, C l , N02

VI.A.3-22 M. P. Doyle, B. S i e g f r i e d , and J . F. D e l l a r i a , Jr., J . Org. Chem., 42, 2426 (1977).

M-»h

t-BuONO, CuX. CH3CN

OH

X = C l , Br

'^60-90% R = N0 2 , C0CH3, C00H, halogen, alkyl

VI.A.4-1

T . - L . Ho, Synth. Commun., 7_, 393 (1977).

RNH.

OCOR'

RNHCOR'

R' = Me, Et, Ph R = Ph, Bz, c-Hx, etc.

73-98%

Also works with pi peri dine. 353

ORGANIC SYNTHESIS-1977 VI.A.4-2

M. K. Sahni et_ a l ^ , Synth. Commun., ]_, 57 (1977). 0 11

, R'-C-O-(salicylic acid/formaldehyde EoLffOET) +

R-NH2

0 M R-NH-C-R'

R' = Me, Ph R = H, Ph, CH 2 C00Et

α,80%

VI.A.4-3 A. Basha, M. Lipton, and S. M. Weinreb, Tetra­ hedron Lett., 4171 (1977). 0 ||

9 ~ MeJUNITIT

º

R-C-O-R

0 || >~

9

~

R-C-NRV

CrLClp R = Ph, Bz, a l k y l , a r y l , conjugated, e t c .

^70-80%

R1= Me, Et R 2 ,R 3 = H, a l k y l ,

VI.A.4-4

cyclic

I . Butula e^ ajk_, S y n t h e s i s , 704 (1977).

ks>k|\|/ | 0=C

ö-T"^ 2. H N R V

R1 = E t , Ph, Bz R2 = H, E t , n - a l k y l , ^-Hx

354

R -O-C-Nv \

R

3

USEFUL SYNTHETIC PREPARATIONS

VI.A.4-5

R. Mukherjee, Indian J. Chem., 15B, 502 (1977). S

ill / R-C-N. \

Θ Θ

D2

R

0

Me 3 0 BF 4

i l / R-C-N. \

3

R's = Ph, alkyl

VI.A.4-6

X 3

^60-80%

J. Palecek and J. Kuthan, Z. Chem., Γ7, 260 (1977), //

1.

NaOH, TEBA

2.

R-X

C

i "2>n

\ n = 3,5,7

RX = Me 2 S0 4 , BzBr, BuBr, etc.

Wn

)

\

Widely varying yields (15-73%)

A. Basha, J. Orlando, and S. M. Weinreb, Synth. VI.A.4-7 Commun., ]_, 549 (1977).

r

1. HCHO

R-C-N.

\

2. NaCNBH 3 , TFA

0

R'

R-C-N Me 50-97%

R = alkyl, aryl R'= H, except for I

\

^N^O

I

H 355

ORGANIC SYNTHESIS-1977 VI.A.4-8 J . D. E l l i o t t and J . H. Jones, J . Chem. S o c , Chem. Commun., 758 ( 1 9 7 7 ) . 0

II -C-O-t-Bu

ꮩ/ï C-OMe R-Br

y

R = Bz, CH2C02Et

VI.A.4-9 (1977).

^70%

G. Helmchen et_ a l ^ , Angew. Chem. I n t . Ed., 1 6 , 728 —

n /? R-C x

n Pb(OAc), ÎU-

I

/? R-C x

° || R-C-NHBz

BzNH? ß-ê

I

NHNHTs

N=NTs

R = Me, t - B u , Ph

VI.A.4-10 (1977).

R-NH-Boc

Widely varying y i e l d s .

D. C. Owsley and J . J . Bloomfield, Synthesis, 118

r-^ jy>-N02

0 jp=\ || -NHCCH3

Fe, CHgCOOH J

" R

R R = Me, OEt, Cl

%70-90X

356

USEFUL SYNTHETIC PREPARATIONS

VI.A.4-11

T.-L.

£^«0;

Ho, J . Q r g . C h e m . , 42., 3755

(1977).

RCOOH

-@L

RCONH Mo(CO),

R = H, Me, OMe, C0CH 3 , CH=CHPh

46%

(R = C0CH 3 )

85%

(R = OMe)

VI.A.4-12 A. Basha and S. M. Weinreb, Tetrahedron Lett., 1465 (1977).

AlEt. R'-CNHCH20H

,Ί D Benzene, reflux

R'-C-NHCH9Et 2 56-94%

VI.A.4-13

Y. Inamoto et al., Synthesis, 632 (1977).

C-H

Br 2 , H 2 S0 4 CH3CN

C-NHAc

^90%

357

ORGANIC SYNTHESIS-1977 VI.A.4-14

R. W. Turner et a l ^ , Synthesis, 31 and 33 (1977). 0 CH,

CH. 1. NaH 0—C—C-NH.

jg)-NH-C- C-OH

2. H20

CH30

CH0

R = N0 2 , CF 3 , COPh, e t c .

^65%

VI.A.4-15 H. Driguez, J . M. Paton, and J . Lessard, Can. J . Chem., 55, 700 (1977).

R0-C-NHC1 chromous chloride

AcO

Cl

79%

VI.A.4-16

S. Wadia et aj^, Synthesis, 35 (1977).

R-CN, CH 2 C1 2 75% HC10,

~«^V o=c

X = H, OH <30-40%

R = Me, Ph

358

NHC00R

USEFUL SYNTHETIC PREPARATIONS

VI.A.4-17 K. A. Parker and J. J. Petratis, Tetrahedron Lett., 4561 (1977). ?Et

CH

HO

H

YEt

F

\ /

Y

NEt2

/ \ R

C0NEt2

|J

i

* R.

A

R R,R' = c y c l i c , H, s t e r o i d a l , alkyl

VI.A.5-1

50-92%

T. Mukaiyama etaL_, Chem. Lett., 635 (1977).

i. f é î ]

G Ts

° >

Me

ROH

Et N

3

H

·-

R-N 3

?/pd

or L i A 1 H

2. LiN 3

y

R-NH 2

4

R = 1°,2°, allylic

VI.A.5-2 (1977).

R'

75-94%

A. Baiker and W. Richarz, Tetrahedron Lett., 1937

R-OH

HNMe ? , 230° CuO, Cr 2 0 3 , Na 2 0

R = long chain alkyl

»-

R-NMe 2 96%

359

ORGANIC S Y N T H E S I S - 1 9 7 7 VI.A.5-3

N. L . H o l y , S y n t h . Commun., £ , 5 3 9 ( 1 9 7 6 ) .

Θ

Me 2 N=CH 2

Θ

0C0CF 3

R-MgBr

»

RCH 2 NMe 2

R = Ph, Tolyl, n-Bu

VI.A.5-4

72-85%

U. Sch'ollkopf e ^ a j ^ , Liebigs Ann. Chem., 40 (1977).

NH~ | R-C-H |

>-

>-

NC | R-C-H |

H

H

1 . BuLi y 2. R'Br

NH9 | ά R-C-H | R

3. H 3 0®

R = H, Ph, v i n y l , 4 - p y r i d y l

'

Up to 65% ( l a s t 3 steps)

Also works w i t h a z i r i d i n e s .

VI.A.5-5 M. B o t t a , F. DeAngelis, and R. N i c o l e t t i , Synthesis, 722 (1977). R1 \ NH +

. R -OH

( t - B u O ) J \ l , Ra-Ni -

/ R^ R1 = H, Me^ 3Î ) R^ = Ph, J} cycl i( R3 = n-Pr,

R1 \

■

~ N-RJ 2 / R^ >94%

i-Pr

360

USEFUL SYNTHETIC PREPARATIONS

VI.A.5-6 A. Zwierzak and J . B. P i o t r o w i c z , Angew. Chem. I n t . E d . , 1(6, 107 (1977). 0 1. R-NH9 ά

II

0

(EtO)pPH

2. 2. R'X, NaOH, NaOH,

y

|| (EtO)?PNRR'

HC1

/ -

R

K

HN

·

HC1

\ .R',

Bu 4 N® HS04® R = E t , Bz, £-Hx

>80%

R' = 1° a l k y l

VI.A.5-7

G. Charles et^ a^L , Tetrahedron L e t t . , 3469 (1977). CH ? 0, CH^OH -—y

R-NH2

R-N(CH20CH3)2

NaCNBH^

R = steroidal

R-NMe2 ^90%

VI.A.5-8 B. S. Cowlagi, M. A. Dave, and A. B. Kulkarni, Indian J. Chem., 14B, 904 (1976).

Ar-N0?

c

MeOH, ChLO ^ H 2 , Ra-Ni

Ar-NMe? ^60%

VI.A.5-9 (1977).

Y. Tamura, J . Minamikawa, and M. Ikeda, S y n t h e s i s , 1

Review:

" ^ - M e s i t y l e n e s u l f o n y l h y d r o x y l a m i n e and Related Compounds—Powerful Aminating Reagents"

361

ORGANIC SYNTHESIS-1977

VI.A.5-10

Y. Kikugawa and M. Kawase, Chem. L e t t . ,

1279 ( 1 9 7 7 ) .

R

^ Ã ^ Í Â Ç 3 , EtOH

\

r - M n 11 L-INUM

\ CHNHOH

10% HC1

/ R'

R'

R = 1° a l k y l ,

74-92%

aryl

R'= H, 1° a l k y l

VI.A.5-11

N. H. Khan e t a ] ^ , S y n t h . Commun., 7., 71 ( 1 9 7 7 ) .

H 9 , Pd/C R-CH=NNHPh

y

RCH2NH2

EtOH, NH 3 ^50-80%

VI.A.5-12 (1977).

E. P. Kyba and A. M. John, Tetrahedron Lett., 2737

N

3

°R"

RXR1

1. LiAlH4, Et20

2. H20

R = Ph, t-Bu, chx,

" R^R 1 >83%

- ( C H j . - , etc. R'= H, Me,

ψ

ά

D

362

USEFUL SYNTHETIC PREPARATIONS

VI.A.5-13 M. Cinquini and F. Cozzi, J. Chem. Soc., Chem. Commun., 723 (1977).

Me

0

R

N = c/

-
*I

1. LiAlhh Ph

H-C-NH.

2. H®, MeOH

I

Ω

Ph R = Me, E t , á-Naphthyl

^40-60% o v e r a l l 57-80% ee

VI.A.5-14 M. C h a s t r e t t e , G. A x i o t i s , and R. Gauthier, Tetra­ hedron L e t t . , 23 (1977).

R0CH2-C=N

-άάU

R \ / R'

R = Me, Et, cyclic

Γ - M Mv

U

IN l l

R1

1. R"M'

·>

2. H 9 0

M = MgBr, Li

'

R-C-NH R" 53-78%

R'= Me, n-Pr, n-Bu, ally! R"= n-Bu,

allyl

VI.A.5-15 A. Zwierzak and I. Podstawczynska, Angew. Chem. Int. Ed., 16, 702 (1977).

0 Ph 2 PNH 2

R-X, NaOH PhH, phase-transfer cat.

0 Ph 2 PNHR HC1 THF

R,R* = 1°,2° alkyl, allyl, Bz

NH 2 R ^40-80%

363

R'X, NaOH PhH, phase-transfer cat.

0 Ph2PNRR' HC1 THF NHRR' ^42-80%

ORGANIC SYNTHESIS-1977 VI.A.5-16 G. H. Posner and D. Z. Rogers, J . Am. Chem. S o c , 99, 8208 and 8214 (1977). — NHBu

n-BuNH, A1

2°3

« ^60-70%

Reaction f a i l s w i t h cyclooctene oxide and l a r g e r r i n g s .

VI.A.5-17 (1977).

A. I . Meyers and R. Gabel, J . Qrg. Chem., 42, 2653 —

COOMe

NR 2

NRC

MeOH

41-98%

Y = H , OMe

R = H, E t , i - P r ,

t-Bu

VI.A.5-18 C. J u t z , A. F. K i r s c h n e r , and R.-M. Wagner, Chem. B e r . , 110, 1259 (1977). C104

1 © ^

^

^R3

NaBH,

R's = Me, Bu, c y c l i c , Ph, Het

Rl

^60-80%

364

USEFUL SYNTHETIC PREPARATIONS

VI.A.5-19

K. Niedenzu, Pure and Appl. Chem., 49, 745 (1977).

Review:

"The Aminoboronation Reaction"

VI.A.5-20 G. W. Gribble, R. W. Leiby, and M. N. Sheehan, Synthesis, 856 (1977). R. \

C=N0H

NaBHd/R"C00H

R \

+

/

CH-N-CH0R" 2

/

R' R,R'

OH |

R' = H, Me, E t , t-Bu,

Ph, Bz,

R" = Me, E t ,

VI.A.6-1 (1977).

36-87%

i-Pr,

E. L.

-(CH2)5n-Pr

Compere, J r .

,JΩ-™

1.

and D. A. W e i n s t e i n , S y n t h e s i s ,

KOH, L i N H 2 ,

MeOCH 9 CH 9 OH ά

ά

2. HC1 CHBr 3 + NH 3

852

ιι

D

"

CH2C00H NH

3

' NH40H

2

R = H, Cl, F, Me, OMe

33-83%

365

ORGANIC SYNTHESIS-1977 VI.A.6-2 N. H. Khan, A. A. S i d d i q u i , and A. R. Kidwai, Indian J . Chem., 15B, 573 (1977).

|jNHPh

H 2 , Pd/C

"["z y

R-C-COOH

R = alkyl, aryl, etc.

R-CH-COOH

Widely varying yields.

VI.A.6-3 T. Iwasaki and K. Harada, J. Chem. Soc., Perkin I, 1730 (1977). J "? PhCH2N=C-C00R2

. 1. R3X, e l e c t r o l y s i s 2

H

pd/c

;

R1 H2N-C-C00H R

R1 = Me, H

36-86%

R2 = E t , Bz

R 3 = Me, Et, Bz, CH 2 CN, CH 2 C00Et

VI.A.6-4 M. D. Fryzuk and B. Bosnich, J. Am. Chem. Soc., 99_, 6262 (1977). — R Chiral Rh(I)phosphine HOOC^

NHCOMe

W^ THF

R = H, Ph, alkyl, etc.

CH 2 R ' H00C-CH-NHC0Me 74-100% ee

366

USEFUL SYNTHETIC PREPARATIONS VI.A.6-5 (1977). /

W. S. Knowles et aj_^, J. Am. Chem. S o c , 9£, 5946 — H C 0 R I

Ph-CH=C

H 2 , MeOH [Rh(l,5-C0D)bisphosphine]®

PhCH2CHC00R ®BF 4

NHCOR'

COOR R = H, Me

23-96% ee

R* = Me, Ph

VI.A.6-6 J . J . F i t t and H. W. Gschwend, J . Org. Chem., 42_, _ 2639 (1977).

v

OMe

OMe

/\

R-CHCOOH

H

NMe 0

I

R-CHCOOMe N=CHNMe.

NH0 R = H, Ph, Bz, CH3SCH2CH2

^80-90%

1. LDA 2. R'X R'

I

R' HC1 R-C-COOMe

R-C-COOH

N=CHNMe.

NH0 60-90% R'X = M e l , j ^ - P r l , ethylene o x i d e , cinnamyl bromide, £-ch1orobenzyl c h l o r i d e , e t c .

367

ORGANIC S Y N T H E S I S - 1 9 7 7 VI.A.6-7 (1977). CHO | CHO

S. G. Ramaswamy and E. Adams, J . O r g . Chem., 42_, 3440 — CHoCOOH H0 V HO I 1. -C09 NaBH, + C=0 —y ! 2. NH OH HO^N^COOH COOH H COOH

-tx

26-41% A one-pot synthesis of 4-hydroxyproline.

VI.A.6-8 D. Ben-Ishai, R. Moshenberg, and J . Altman, Tetra­ hedron, 33, 1533 (1977). R

R.

\

NSA C=CH,

MeOCHCC)0Me

+

benzene,

1

)R" NHCC

/

BF

3

—*

A

\

/

C=CH-CH-C00Me

R'

R1 \ ^

1

NHC0R"

^COOMe

Ph R' \ /

R*

C=CH 2

+

H0CHC00H

H 2 S0 4 ,

NHCOR"

dioxane

°v>>—NHCOR"

R,R* = H, Me, Ph, OMe, OAc R" = Ph, PhCH20 The above products are converted by standard methods to the corresponding amino acids.

368

USEFUL SYNTHETIC PREPARATIONS VI.A.6-9

K. Achiwa, Chem. Lett., 777 (1977).

Use of APPM and PPPM as chiral biphosphine ligands in the asymmetric synthesis of (R)- and (S)-N-benzyloxycarbonylalanine. Ph2P APPM, R = CH 3 C0CH 2 PPh 2

PPPM, R = (CH3)3CC0-

Yields are 85-95%, with 59% ee for (R) and 21% ee for (S)

VI.A.7-1 D. J. Burton and J. L. Hahnfeld, J. Org. Chem., 42, 828 (1977). — -116° CFC13

+

n-BuLi

+

olefin

THF, hexane F

Cl

0-49%

CFBr3

+

ni-BuLi

+

-116°

olefin

THF,

hexane

F

Br

0-73%

369

ORGANIC SYNTHESIS-1977 VI.A.7-2

M. Fedorynski, Synthesis, 783 (1977).

\ \

/

HCBr 9 Cl, 50% NaOH l

>=< /

\

/

—C

*

C-

\

Dibenzo-18-crown-6

/ C

/ \ Br

Cl

^50-70%

VI.A.7-3 R. A. Abramovitch, V. Alexanian, and J. Roy, J. Chem. S o c , Perkin I, 1928 (1977).

PhS0 2 CHN 2

heat or hv

y

PhS0 2 CH:

L. T. Scott and M. A. Minton, J. Org. Chem., 42^, 3757 ' —

VI.A.7-4 (1977). 0

R-C-Cl

CH 2 N 2 , Et3N Et 2 0, -78°^-25°

R = alkyl, Bz

0 R-C-CHN 86-96%

Requires only one equivalent of ChLN 2 .

370

2

USEFUL SYNTHETIC PREPARATIONS

VI.A.8-1 L. Duhamel and J . - M . P o i r i e r , J . Am. Chem. S o c , 99_, 8356(1977). —

Y

Y

i

n-BuLi

Y

|

C-Br

E-X

',

C-Li

1

z'

/

I

^45-65% E-X = H 2 0, Mel, EtI, Bui, \

v

MeCHOH-CHO

VI.A.8-2 F. M. Laskovics and E. M. Schulman, J. Am. Chem. S o c , |£, 6672 (1977).

0

A...

N

X A

Çfi2 > 2


º

R

R

R'

R'

]N

n

-

CC13CCC13 R

R' ^90%

VI.A.8-3 H. G. Viehe, B. LeClef, and A. E l g a v i , Angew. Chem. I n t . E d . , 16, 182 (1977).

R_CH

2CC1

. M EtoN

r

ό

+

R. \

/ C=C

.NMe, 2

/

\

0=C I Cl

Cl9C=NMe9 2 Ö 2 R = Me, E t , C l , Ph

60-75%

371

Cl

ORGANIC SYNTHESIS-1977 VI.A.8-4 H. L. Yale and E. R. S p i t z m i l l e r , J . Het. Chem., U_9 1419 (1977). —

^ /

N H

H2N

2

yzzCHCOOEt R'' —

— R —ts 'ß > C H C 0 0 E t "S^

R1

11-78%

R = Me, Br, Cl R'= Me, Ph

VI.A.8-5 M. P u l s t , S. S t e i n g r u b e r , and E. K l e i n p e t e r , Z. Chem., V7, 93 (1977). ê ç ^ ^ Í

-HO

I]

+ HNRR*

×

>

Ph^CHO

Ph

R,R' = Me, E t , Bz, - ( C H 2 ) 4 - , e t c .

^

ß ^CH-NRR'

25-89%

VI.A.8-6 B. de Jeso and J . - C . Pommier, J . Chem. Soc., Chem. Commun., 565 (1977). P a r t i a l methanolysis o f o r g a n o t i n or -magnesium s a l t s o f imines leads to secondary enamines which are s t a b l e i n a p r o t i c media.

VI.A.8-7

J . V. G r e e n h i l l , Chem. Soc. Rev., 6_, 277 (1977).

Review:

"Enaminones"

372

USEFUL SYNTHETIC PREPARATIONS VI.A.9-1

S. Holand and R. E p s z t e i n , S y n t h e s i s , 706 (1977) R'

R' T s C l , NaOH

R-C-CHR"

R-C

CHR"

glyme HO OH

0 55-85%

R,R" = H, a r y l , a l k e n y l , a l k y n y l R1 = H, Ph

VI.A.9-2 G. A. Kraus and M. J. Taschner, Tetrahedron Lett., 4575 (1977).

°-

LiCH2C00Et

0 |

R

1 . 2 LDA OEt

R ^ R '

R'

R = Ph, n - a l k y l ,

OH

v^ yx

Y. Tamura et^ aj_^, S y n t h e s i s , 693 (1977).

©

Ph-S-CH -S-i 2R

I

© N-Ts

COOEt

31-48%

olefinic

R' = H, Me

VI.A.9-3

0

1. NaH, THF 2. PhCHO

\A/

PK

45-80% ^90% trans

373

ORGANIC SYNTHESIS-1977 VI.A.9-4 (1977).

P. Sundararaman and W. Herz, J . Org. Chem., 4 ^ , 813 —

R'

f™

R

R*

CrO, pyridine

H

* 0

R,R' = a l k y l , c y c l i c

50-81%

VI.A.9-5 I . G. Tishchenko, V. N. S y t i n , and I . F. R e v i n s k i i , J . Org. Chem. (USSR), 1 3 , 1062 (1977). 0 1. RMgX Hx-C-CH=CHNMe

2

Hx-C N

v

2. H 2 0 2 ,

È

0Ç

R = 1 ° , 2 ° , 3 ° aIlkkyyl 1 l

V ^80%

VI.A.10-1 A. R. K a t r i t z k y et a l . , J . Chem. S o c , Chem. Commun., 701 (1977).

RCH2NH2

© BF, È 2.

R'COONa

R = a l k y l , Bz, p i c o l y l

R-O-C-R' ^60-70%

R' = Me, Ph

374

USEFUL SYNTHETIC PREPARATIONS VI.A.10-2

M. Yamashita et a l ^ , Cheiti. L e t t . , 1355 (1977). Fe(C0)5 ^

Q

R 0 ^ + R'X R = Ã , 2 ° a l k y l , Bz

0 || R'-C-OR 20-80%

R'= 1° a l k y l , CH2C00Et X = I , Br

VI.A.10-3

M. K. Sahni et aJK_, Synth. Commun., ]_, 57 (1977). 0 11

R-OH

, R1-C-0-(salicylic acid/formaldehyde eoljmier) y

R = Me, Et, Bu

VI.A.10-4

R' = Me, Ph

0 M R_QJ\_Rt %80%

S.-S. Wang et^aJL, J. Org. Chem., 42, 1286 (1977). 1. Cs 9 CO q ^—^ 2. BzBr

R-COOH (an amino acid)

R-COOBz ^70-90%

VI.A.10-5 A. R. Banks, R. F. Fibiger, and T. Jones, J. Org. Chem., 42, 3965 (1977). o

CH 2 =C(CH 3 )C0C1 + ROH

3 A molecular sieves >- CH 2 =C(CH 3 )C00R

R = cyclopentyl, 3°alkyl, Ph

^80-90%

375

ORGANIC SYNTHESIS-1977 VI.A.10-6 J . C. C h o t t a r d , E. M u l l i e z , and D. Mansuy, J . Am. Chem. S o c , 9£, 3531 (1977).

R-CH2CH2CH20H

trans-[PtC1o(C?HjAcIm] ά

Arlm =

ά

/

X

Me^

R-CH2CH2CH20Ac

Ac MC

Me

fi

■

\

^

R = Ph,

4

a.70%

y

'N

VI.A.10-7 0. Achmatowicz, J r . and G. Grynkiewicz, Tetrahedron L e t t . , 3179 (1977). 0 COOH || 0 P P h v H00C-C-C00H /r^\ \\

R-OH

+

,<Äs

*

y benzene

$kD/—C-°R

^.^íôß/

R' %50-80% R = b e n z y l , menthyl, o c t y l

VI.A.10-8

( i n v e r s i o n on R)

S. Inaba and I . Ojima, Tetrahedron L e t t . , 2009 (1977) OMe 1. T i C L · , CH9C19

/

2RR'C=C \

0SiMeo

2.

H90 ω

>

RR'C-COOMe

I RR'C-COOMe 73-80%

R,R' = H, Me, Ph, -(CH2)g-

376

USEFUL SYNTHETIC PREPARATIONS VI.A.10-9 (1977).

W. L. Mock and M. E. Hartman, J . Qrg. Chem., 42, 459 —

0 Il C R

Et 0 +

N9CHC00Et

BF4U 5->-

R1

0 COOEt || X^ CHR'

A study of the synthetic scope of this reaction.

VI.A.10-10 S. C. Auteri, D. W. Cameron, and C. B. Drake, Aust. J. Chem., 30, 2479 and 2487 (1977). 0

{X

0-C-R

OH RCOOH

0S02R'

R'S03H

OH

R = long-chain alkyl

Widely v a r y i n g y i e l d s .

R'= Ph, t o l y l , m e s i t y l , e t c .

VI.A.10-11

J . E. Herz e t a L . , Synth. Commun., £ , 383 (1977) 0 OH

OCR

C=CH 1. TlOEt

VX\NCECH

2. RC0C1

R = 1-adamantyl, CMe^-Bu

377

70-80%

ORGANIC SYNTHESIS-1977 VI.A.10-12 (1977).

J . H. Clark and J . M. M i l l e r , Tetrahedron L e t t . , 599 0

II

oo

Br-CH ? -C-Ph KF, DMF

R-C00H

·-

|| || R-C-0-CH?CPh %c

R = Me, E t , t - B u , Ph, e t c .

>90

, VI,A.10-13 S. L. Beaucage and K. K. O g i l v i e , Tetrahedron L e t t . 1691 (1977). 0 0

MTr0

"Y°i h y m i n e R"""°"""R

MTr0

h-fl pyridine or L·., THF 0SiMe 9 -t-Bu

~Wh h

/· I 0-C-R 0II

MTr = £ - m o n o m e t h o x y l t r i t y l

>95%, R= = Me, Ph, )£-Bu 60%, R CH (CH 3

VI.A.11-1

R-OH

2 12

M. Yamashita and Y. Takegami, Synthesis, 803 (1977)

+

R'-X

Ni(acac) ? ^

R,R' = Ph, Bz, n - a l k y l

R-O-R1 65-90%

X = C l , Br

378

USEFUL SYNTHETIC PREPARATIONS VI.A.11-2 M. J . Diem, D. F. Burow, and J . L. F r y , J . Qrg. Chem,, 42, 1801 (1977).

R-OH

+

ROR'

R' 3 0® BF®

^70%

R = 1°,2° alkyl R'= Me, Et

VI .A..11 -3

G. Gelbard and S. Col onna, Synthesis , 113

Resin (Ar-0®) Ar-0-R R-X >90% Ar = Ph, n a p h t h y l , e t c . R = Me, a l l y l , Bu, i_-Pr

VI.A.11-4 G. H. Posner and D. Z. Rogers, J . Am. Chem. S o c , 99>, — 8208 and 8214 (1977).

ROH, A1 2 0 3

R = Me, Bz, a l l y l

F u l l paper, many examples.

379

47-98%

ORGANIC SYNTHESIS-1977

VI.A.11-5

M. Cavazza and R. C a b r i n o , S y n t h e s i s ,

298

(1977),

RONa

OTs

ROH 30-80%

R = E t , Ph

VI.A.11-6

F. J. Williams et al_^, J. Org. Chem., 42!, 3425 (1977).

¹§^ïÈ DMF

P

0

R = H, C l , Me, OMe

65-95%

VI.A.11-7

J.

Emert e t a L _ , J . O r g . Chem., 42., 2012

2 RCHOH

R\

^O^

DMSO 175° X

X

R = H, Me

^90% X = H, F

380

(1977).

^R

USEFUL SYNTHETIC PREPARATIONS VI.A.11-8 K. C. Nicolaou and Z. Lysenko, Tetrahedron L e t t . , 1257 (1977).

G>

OH PhSeCl CH 2 C1 2 , -78°

87%

0> SePh

95%

Q>

Ra-Ni

94%

A general technique for ether formation.

VI.A.12-1

G. A. Olah e^ al_^, Synthesis, 677 (1977) 0

R4Si

+

0 A1C1.

R'-C-Cl

R-C-R'

CH2C12

41-82%

R = E t , n-Bu R'= E t , i - P r ,

VI.A.12-2 (1977).

c-Hx

E. Keinan and Y. Mazur, J . Am. Chem. Soc. , 99_, 3861 — 0

HL

X

R

.NCL

—

basic s i l i c a gel ether

R»

R,R' = H, n - a l k y l ,

cyclic

X

R

R'

^80-90%

381

ORGANIC SYNTHESIS-1977 VI.A.12-3 0 . Possel and A. M. van L e u s e n , T e t r a h e d r o n 4229 ( 1 9 7 7 ) . NaH TosCH9N=C

| Tos-C-N=C I R'

+

ω

Me 9 S0/Et 9 0 2

2

Lett.,

H~0® —-—y

\ C=0 y

R

1 . RX 2. R'X %40-80%

R,R« = 1°,2° a l k y l , Bz, - ( C H 2 ) g X = C l , Br,

VI.A.12-4

H \ /

I

P. A. B a r t l e t t et. aK_, Tetrahedron L e t t . , 331 (1977).

/ C \

R

N09

0 || C

1. jt-BuOK y 2. t-BuOOH,

R

'

V0(acac) 2 ,

/ R

\ R

'

benzene R,R' = H, a l k y l

VI.A.12-5

^50-80%

T. Shono et. aj_^, Tetrahedron L e t t . , 3625 (1977). ?

CHQ0CH9C00Me 3

2

RMgX

c

R n-Pr 1-Pr n-Bu 1-Bu cyclohexyl

>

Hydroxy ether, % 85 70 82 83 48

CH~0CH9C-0H 3 ^ |

R

Ketone, % 85 88 80 80 80 382

R

anodic 0 x i d a t i o n

>

\ C=0 •

R

USEFUL SYNTHETIC PREPARATIONS

VI.A.12-6

B. M. T r o s t and Y. Tamaru, J . Am. Chem. S o c , 99,

1 (1977).

V"

\

1. 2 LDA COOH

.SMe C

2. MeSSMe

'

COOH

NCS

y=o

EtOH

^50-60% overall

VI.A.12-7 T. Mukaiyama, Y. Echigo, and M. Shiono, Chem. L e t t . , 179 (1977).

Il Ph-C-C-R

Cl

I

1

I II

Ph-C-C-R1

Me

HO OH

R

R = Ph, Bz

54-88%

R'= H, Me, Et, Ph, Bz

VI.A.12-8 D. van Leusen and A. M. van Leusen, Tetrahedron Lett., 4233 (1977).

N=C

1. n-BuLi TosCHRN=C

>2. R'COCl

| R-C—COR' | Tos

R = Ph, £-0MePh

m

ΗΛΓ —-

° °

■

|| || R-C-C-R'

^50-70%

R'= Ph, Me, E t , Bz

383

ORGANIC SYNTHESIS-1977 VI.A.12-9 J . B. Hendrickson, K. W. B a i r , and P. M. Keehn, J . Qrq. Chem., 42, 2935 (1977). CH2R'

1. NaH R-CH2-S02CF3

R-CH-S02CF3

2. R'CH2X

1. 2 NaH 2. TosN.

X

Rx

R = Ph, a l k y l R'= a l k y l 1 . P(OEt),

cyclohexane 2. H30

^80%

VI.A.12-10 171 (1977).

M. Asaoka, N. Sugimura, and H. T a k e i , Chem. L e t t . , R2

I^OEt κι^Λ R 2

R

>^o

—r

Ac 2 0

jf\

ITC(OEt),

= Ph, £-CH30Ph

HOAc, H20

= Me, Et

51-83%

384

H,

USEFUL SYNTHETIC PREPARATIONS VI.A.12-11 (1977).

T. E. Cole and R. P e t i t , Tetrahedron L e t t . , 781

jj

3 NMe.-HFeiCOL

R-Ü-C1

"

R CH0

—

"

R = 1°,2°,3° a l k y l , Ar, cycloalkyl,

75-100%

heterocyclic

A. Ohta e t ΰL_9 S y n t h e s i s , 792 (1977),

VI.A.12-12

CrCl 9 ^ CH30H

R-CH9-N09 ά

ά

R-CHO

R = 1° a l k y l

32-66%

VI.A.12-13 L. A. Paquette, W. D. Klobucar, and R. A. Snow, Synth. Commun., 6>, 575 (1976). SPh 1. NaSPH R-CH9X

■

ά

/ R-CH

2. NCS

Na9C0? ±—^

R-CHO

\

R = a r y l , cyclohexyl

Cl ^80%

X = C l , Br

R

\

1 . PhSH, AIBN, hv C=CH„

f R

ά

R. >-

2. HgCl 2 , CdC03

R,R' = H, a l k y l , c y c l i c

CH-CHO R

/

24-43%

385

ORGANIC SYNTHESIS-1977 VI.A.12-14

W. E r t e l and K. F r i e d r i c h , Chem. B e r . , 110, 86 (1977). H \

Ar-H

rOOEt

/ C=C / \

+ Cl

1. A1C12. H90 *

Y

Ar-CHO ^40-60%

Y = COOEt, CN Ar = subst. Ph, n a p h t h y l , e t c .

VI.A.12-15

P. Magnus et. a l ^ , J . Am. Chem. S o c , 99, 4536 (1977). Li

0

A

R

R,R'

CICHSiMe

H 3.

SiMe 3

R

3

2

,

C

MeOH R

R'

= H, P h , c y c l o a l k y l

VI.A.12-16

R

R'

H

^80-90%

^70-90%

G. D o l e s c h a l l , Tetrahedron L e t t . , 381 (1977). P

R-CH2-C00H

CHO

y

>-

\

2 VN / Ph

R = a l k y l , Me00C-(CH2)3-,

Ph

SMe

^N R-CH—( ©J

|

°

AC

VN p'h

PhC0(CH2)2R-CHO 31-56% o v e r a l l 386

SMe

USEFUL SYNTHETIC PREPARATIONS VI.A.12-17 P. C. Traas, H. J . Takken, and H. Boelens, Tetra­ hedron L e t t . , 2027 (1977).

R\

P0C1, DMF

R ^ ^ 0

R

S^

C H 0

II

H9, Pd/C

* ^

R,R' = c y c l i c , Bz, cyclopropyl,

C H 0

60-95%

jT-al kyl

VI.A.12-18 (1977).

S. Murai et a l . , Angew. Chem. I n t . Ed., 1 6 , 789 —

A

HSiEt2Me CO, Co 2 (C0) 8

f

CH 2 -0SiEt 2 Me

(CH CH 02 ) n CH 2 -CH0

n = 0, 1, 2

^40-50%

VI.A.12-19 J. M. Reuter and R. G. Salomon, J. Qrg. Chem., 42, 3360 (1977). —

c

(PPh 3 ) 3 RuCl ; H

Several additional examples, yields 56-92%.

387

"0

84%

ORGANIC SYNTHESIS-1977 VI.A.12-20 V. Reutrakul and W. Kanghae, Tetrahedron L e t t . , 1377 (1977). 0

0

0

CH^T^CH?

v /

fH0

0^-J-Ph

P"-S-CH2C1

' v ) ~~ v CH

V

\w/„

CH

CH

(CH2)„

^V^

\cH2)n

n = 1-5

40-90%

VI.A.12-21 754 (1977).

V. E. Gunn and J.-P. Anselme, J. Org. Chem., 42_, —

0

00

ArC-CH 2 Br

+

y

Et2N0H

ArC-C-H

+

Ar = Ph, 3-naphthyl,

Et 2 NH-HBr

55-78%

£-BrPh, m-MeOPh

VI.A.12-22 255 (1977).

S. Ncube, A. Pelter, and K. Smith, Tetrahedron Lett.,

s

M = MgBr, Li

^^

R = n-Pr, i_-Pr, chx, Bu, Ph

388

b

USEFUL SYNTHETIC PREPARATIONS

VI.A.13-1 F. Campagna, A. Carotti, and G. Casini, Tetrahedron Lett., 1813 (1977). 0

II

R-C-NH2

(CF.C0)90 - pyridine, rt

y

R-C=N ^70-90%

R == a l k y l , aryl

VI.A.13-2 C. R. Harrison, P. Hodge, and W. J. Rogers, Synthesis, 41 (1977). 0

II R-CNH2

CCl4-PPh2-(p) 4 -"2 y

or R-CH=N0H

R-CEN

76-100%

R = 1° a l k y l , s t e r o i d a l , s u b s t i t u t e d Ph

VI.A.13-3

M. D. Dowle, J . Chem. S o c , Chem. Commun., 220 (1977),

M

R-IV

Et00C-N=N-C00Et

*

R N

^

^60-70%

389

ORGANIC SYNTHESIS-1977 VI.A.13-4 0. H. O l d e n z i e l , D. van Leusen, and A. M. van Leusen, J . Org. Chem., 42, 3114 (1977). H

n H

\

C=N-CH2Ts

R-^^R'

0 Î Í

\ S

i-BuOK

R

R,R' = c y c l i c , Ph, 1 ° , 2 ° , 3 ° a l k y l

R»

v70-80%

VI.A.13-5 D. M. Orere and C. B. Reese, J . Chem. Soc., Chem. Commun., 280 (1977). 0 ||

1.

(i-Pr) 3 PhS0 2 NHNH 2 (TPSH)

C

/ R

y

\

2. KCN, MeOH, r e f l u x

/ R

R'

R,R' = H, a l k y l , c y c l i c

VI.A.13-6

C \ R'

47-74%

C. Bernhart and C.-G. Wermuth, S y n t h e s i s , 338 (1977).

fi

CH CN

3

N X = H, C l , N0 2 , OMe

69-80%

390

USEFUL SYNTHETIC PREPARATIONS

VI.A.13-7

T. Kametani et aj_^, Synthesis, 245 (1977).

uC"2

V T ^

cuci

·°? , or C s

pyridine

κ ^

R = H, OMe, OBz, e t c .

VI.A.13-8

35-41%

J. K. Rasmussen, Chem. Lett., 1295 (1977).

PhCH=N0H

KCN, 18-crown-6 Me^SiCl 0

y

Ph-CN ^40-50%

VI.A.13-9 K. Yamamura and S.-I. Murahashi, Tetrahedron Lett., 4429 (1977). D

U

\

/ C=C / \ R'

KCN, Pd(PPh) 4 Br

crown e t h e r , benzene

R,R' = H, Ph, Me

■

R \ / R1

C=C

H / \ CN

^80-90%

391

ORGANIC SYNTHESIS-1977 VI.A.13-10 126 (1977).

A. Loupy, K. Sogadji, and J . S. Penne, Synthesis, 0 X2P-CH2CN

R-CHO

R-CH=CHCN

y

THF or DMF X = OEt or Ph

R = a r y l , j_-Pr

^90%

VI.A.13-11 C. L. Liotta, A. M. Dabdoub, and L. H. Zalkow, Tetrahedron Lett., 1117 (1977).

Me 2 C

, KCN CN

18-crown-6, benzene or ChLCN

VI.A.13-12

K. Yoshida, J . Am. Chem. S o c , 99_, 6111 (1977)

Or

R'

f

NaCN, MeOH

^Or»'

NC

anodic electrolysis

R (CN may be on one of the methyl groups)

R = Me, Ph R'= one or more Me,

Widely varying yields.

benzo (indoles)

392

USEFUL SYNTHETIC PREPARATIONS

VI.A.13-13 2001 ( 1 9 7 7 ) .

F. E. Z i e g l e r and P. A. Wender, J . O r g . Chem., 4 2 , —

0

NNHC00CH„ CN

C.

/

\

NFLNHC00CH-.

.... cat. HOAc

HCN

C.

'

C-NHNHCOOCH-

/ \

MeOH

3

/

MeOH, rfx Br2/CH2C12 NaHCOo

CN

\

VI.A.13-14

F.

CN

/ c

MeOH

'C-N=NCOOCH,

NaOMe

Pochât, Tetrahedron L e t t . ,

CH(SEt)<

I2,

3813

Hg(CN)2

CH3CN

(1977).

M~

SEt

CH

R

68-93%

1.

Br0

2 . DMSO

M-

C-CN

70-90%

393

ORGANIC SYNTHESIS-1977 VI.A.13-15 A. N. Volkov and A. N. N i k o T s k a y a , Russ. Chem. Rev., 46, 374 (1977). Review:

VI.A.13-16 (1977).

"a-Cyanoacetylenes"

G. Skorna and I . U g i , Angew. Chem. I n t . E d . , 1 6 , 259 — 0

A

ci

occi3

(diphosgene) R-NH-CHO

y

R-NC

R = Me, t - B u , c-Hx, Bz, Ar

VI.A.13-17 275 (1977).

47-98%

G. Domschke, R. Beckert, and R. Mayer, Synthesis, CHCU, KOH

R-N=S=0

*

R-N=C

Benzene R = a r y l , cyclohexyl

>75%

394

USEFUL SYNTHETIC PREPARATIONS

VI.A.13-18 Y. Echigo, Y. Watanabe, and T. Mukaiyama, Chem. Lett., 697 (1977).

ΟΦ-

Cl

I " BF d 4 Et

RNHCHO

Et 3 N

y

R = 1°,2° alkyl, aryl, Bz

VI.A.14-1

RNC 69-81%

G. Gelbard and S. Colonna,» Synthesis,

Res in-(NO®) -|-

R-N0 2

R-X Yield, %

R-X MeCHCOOEt

95

Br Me2C-C00Et

60

Br n-BuBr

47

i-PrBr

29

Bz-Br

87

395

ORGANIC SYNTHESIS-1977 VI.A.14-2 I. Sh. Shvarts et aj^, Bull. Akad. USSR Chem., 25_, 1589 (1977). — OSiMe.

Θ Θ N0 2 BF 4

37-90%

VI.A.14-3 V. Jager and J. Gόnther, Angew. Chem. Int. Ed., 16_, 246 (1977). — I N 2 0 4 /I 2 02N *(CH2)^ Ether, 0°C <) ;

2n

n = 2,3,4

VI.A.14-4

>80%

H. Suzuki, Synthesis, 217 (1977).

Review:

"Side-Reactions i n Aromatic N i t r a t i o n : Some Synthetic Aspects"

VI.A.15-1 D. Cech and A. Holy, C o l l . Czech. Chem. Commun., 42_, 2246 (1977). — Review:

"Preparation o f 2-Pyrimidone Nucleosides from U r a c i l

Nucleosides"

396

USEFUL SYNTHETIC PREPARATIONS VI.A.15-2

R. L. Shone, Tetrahedron L e t t . , 993 (1977). 0

0SiMe 3

N *Í.|\Ç

I^OSiMe3

NH

11 II

Bz

°—I

I

S ^ °

2. CH30H, ^O^^Ph

Amberlite IR-45

.

âæ0

n

ÂæÏ

. OBz

n

50-75% for d i f f e r e n t bases

VI.A.15-3

F. Ramirez e t a l ^ , J . Org. Chem., ^

3144 (1977).

Synthesis of d e o x y r i b o o l i g o n u c l e o t i d e s by means of c y c l i c enediol pyrophosphates formed using di(1,2-dimethylethenylene)pyrophosphate.

VI.A.15-4

R. Youssefyeh et_ a j ^ , Tetrahedron L e t t . , 435 (1977)

" S y n t h e t i c Routes t o

4'-Hydroxymethylnucleosides"

based on the a l d o l c o u p l i n g o f

furanose-5'-aldehydes

w i t h formaldehyde accompanied by Cannizzaro r e d u c t i o n by excess formaldehyde.

VI.A.15-5 J . - L . Fourrey, G. Henry, and P. J o u i n , J . Am. Chem. S o c , 9£, 6753 (1977). Use of a p y r i m i d i n e S-nucleoside

photorearrangement

i n a m u l t i s t e p synthesis o f pseudonucleosides.

397

ORGANIC SYNTHESIS-1977 VI.A.15-6

F. Ramirez e t a l . , Synthesis 451 (1977).

A p p l i c a t i o n o f C y c l i c Enediol Pyrophosphates to the Synthesis o f Deoxyribonucleotides.

VI.A.15-7 (1977).

S.Y.-K. Tan and B. F . - R e i d , Can. J . Chem., 55^, 3996 —

" S y n t h e t i c Routes t o 2' ,3'-Cyclopropanated and 2 ' , 3 ' - U n s a t u r a t e d Nucleosides"

VI.A.15-8 R. R. Schmidt, J . Karg, and W. G u i l l a r d , Chem. B e r . , 110, 2433 (1977). "Synthesis o f Pyrazole Nucleosides via Ribosylhydrazines"

VI.A.15-9 T. K. Bradshaw and D. W. Hutchinson, Chem. Soc. Rev., 6_, 43 (1977). Review:

" 5 - S u b s t i t u t e d Pyrimidine Nucleosides and Nucleotides"

VI.A.15-10 (1977). Review:

V. Amarnath and A. D. Broom, Chem. Rev., 77_, 183 — "Chemical Synthesis of O l i g o n u c l e o t i d e s "

398

USEFUL SYNTHETIC PREPARATIONS VI.A.16-1 M. P. Doyle, S. B. W i l l i a m s , and C. C. McOsker, Synthesis, 717 (1977). R' R-CH2-CH-0

BF 3 -Et 2 0 100c

R's = a l k y l , c y c l i c

R-CH=CH-R'

63-89%

VI.A.16-2 G. W. Francis and J . F. Berg, Acta Chem. Scand. B, 3 1 , 721 (1977).

CuSCL -C—C-

I I

HO

180e

^c-c^

H

^45-90% for secondary alcohols

VI.A.16-3 G. H. Posner, G. M. Gurria, and K. A. Babiak, J. Org. Chem., 42, 3173 (1977).

A 1 ? 0 3 , 25° 24 hr, Et 2 0 ^60-80%

X = OMs, OTs

Substrates are c y c l o a l k a n e s , s t e r o i d s , and open-chain alkanes

399

ORGANIC SYNTHESIS-1977 VI.A.16-4

R-H

+

R. Tanikaga e ^ al^, Synthesis, 299 (1977). 0 || H9C=CH-S-Ph ά

1. Base, THF * 2. H 2 0 3.

R-CH=CH9

Δ

R = SPh, OBz, p y r i m i d i n e ,

^70% o v e r a l l

a l k y l c o n t a i n i n g cyano, k e t o , n i t r o , and carboethoxy groups

VI.A.16-5 (1977).

M. Kim and J . D. White, J . Am. Chem. S o c , 9£, 1172 —

°W;S-N J! « CH 0 | ty 0 3 L \ H f ..u CH o \ Ι.,ιΗ h\l^

Me o S0, ' Τ ^

53% i s o l a t e d

VI.A.16-6

T . - H . Chan, Accounts Chem. Res., 10., 442 (1977).

Review:

"Alkene Synthesis v i a

3-Functionalized

Organosilicon Compounds"

400

USEFUL SYNTHETIC PREPARATIONS

VI.A.16-7 E. W. C o l v i n and B. J . H a m i l l , J . Chem. S o c , Perkin I , 869 (1977).

0

Λ

Me 3 SiCHN 2

R-C^C-R'

BuLi

R R' R,R' = Ph, Me, H, benzoyl

22-80%

VI.A.16-8 H. Hommes and L. Brandsma, Rec. Trav. Chim. Pays-Bas, 9£, 160 (1977). C 4 H 9 C,C-(CH 2 ) n CH 2 R

NaNH ?

1f3,diamingpropane>

HC,C-(CH 2 ) n + 4 CH 2 R

R = H, OH

a,80-90%

n = 0-5

VI.A.16-9 J. L. Coke, H. J. Williams, and S. Natarajan, J. Org. Chem., 42, 2380 (1977).

1. CH3Li

PX,

2.

X = Cl, Br

Δ

CHQCCH^C(CHQ)oCH^C=CH

70%

401

ORGANIC SYNTHESIS-1977

VI.A.16-10 OAc | HC^CC-R R'

M. M. Midland, J . Org. Chem., 42_, 2650 (1977). Bu \

1 . n-BuLi y

R /

hLO —

C=C=C

2. Bu3B

/

\

Bu2B

R,R' = H, Ph, a l k y l ,

H | Bu-C=CC-R R'

R'

cycloalkyl

60-91%

VI.A.16-11 J . S. K i e l y , P. Boudjouk, and L. L. Nelson, J . Org. Chem., 42, 2626 (1977). — X C=CCH(0Et)2

1. n-BuLi, THF

HCECCH(OEt) 2

^90%

X = Br, I

VI.A. 17-1 M. Waki and J. Meienhofer, J. Am. Chem. S o c , 99_, 6075 (1977). — A study of peptide synthesis using the four-component condensation (Ugi reaction). ΡΊ-000Η 2

+ R CH0

+

H 2 NR ]

+ CN-P

-*·

2

402

P 1 C0-NHCHR 2 C0-NHP 2

USEFUL SYNTHETIC PREPARATIONS VI.A.17-2 S. Nozaki, A. Kimura, and I . Muramatsu, Chem. L e t t . , 1057 (1977). Boc-Ala-OH WSCD-HC1, Et~N I

+ H-Gly-OEt-HCl

Cl

VI.A.17-3

■

Boc-Ala-Gly-OEt

CH 2 -CH 2 ,H 2 0, HOBt Cl

79%

M. K. Sahni et aL_, Indian J. Chem., 15B, 481 (1977).

"Sulphonates of Copoly(ethylene-N-hydroxymaleimide) as Coupling Reagents for Synthesis of Amides and Peptides". The advantages of the polymeric reagent over solution reactions are discussed.

VI.A.17-4 H. Ito, N. Takamatsu, and I. Ichikizaki, Chem. Lett., 539 (1977). Use of Bz-N=C=N-Et in peptide synthesis.

Formation

of N-acylurea and racemization are suppressed rela­ tive to the case using DCC.

VI.A.17-5 T. Teramoto, T. Kurosaki, and M. Okawara, Tetrahedron Lett., 1523 (1977). 0 .

RN

Use o f 3-hydroxyhydantoin, "n. a c t i v a t i n g group i n

V^N-OH IuV. //

0

as an acyl synthesis.

Yields 87-91% f o r simple r e a c t i o n s where R=ChL or i-C4H9.

403

ORGANIC SYNTHESIS-1977 VI.A.17-6

C. DiBello e t aL·., Tetrahedron L e t t . , 1135 (1977).

Use o f DCC/HOBt f o r solid-phase coupling of a r g i n y l peptides.

Yields up to 96%.

VI.A.17-7 G. A. Zheltukhina et a ] ^ , J . Gen. Chem. (USSR), 47., 1112 (1977). — " M o d i f i c a t i o n o f the Azide Method f o r the Condensation of Peptide Fragments on a Polymer".

( A d d i t i o n of N-

hydroxysuccinimide and a gradual increase i n tempera­ t u r e -10->20° over s i x days.)

VI.A.17-8

G. Jung e t a l ^ , Angew. Chem. I n t . E d . , lj>, 642 (1977).

Use of i n s o l u b l e polymer-bound reagents and s o l u b l e peptide c a r r i e r s f o r chain e l o n g a t i o n of p e p t i d e s . No side products are formed i n the actual

coupling

s t e p , and excess reagents do not have to be removed.

VI.A.17-9 M. A. T i l a k and J . A. Hoffman, J . Qrg. Chem., 42., 2098 (1977). — Use of a large excess o f p r o t e c t e d amino a c i d azide i n peptide s y n t h e s i s .

The excess azide subsequently

hydrolyzed and removed, g i v i n g " a n a l y t i c a l l y pure peptides i n high y i e l d s " .

404

USEFUL SYNTHETIC PREPARATIONS

VI.A.17-10

M. Ueki and S. Ikeda, Chem. Lett., 869 (1977),

Use of diphenylphosphinothioyl (Ppt)-amino acids in solid phase peptide synthesis to produce tryptophancontaining peptides.

VI.A.17-11

D. Yamashiro, J. Org. Chem., 42, 523 (1977).

Use of the 4-bromobenzyl group as a side-chain protecting group for aspartic acid and serine and the 4-chlorobenzyl group for threonine in solid-phase peptide synthesis.

Stable to 50%

CF 3 C00H in CH 2 C1 2 , and removed by HF for 10 min at 0°.

VI.A.17-12 (1977).

R. B. M e n r i f i e l d e t aj_^, Tetrahedron L e t t . , 4001

0

Peptide-C00£>

R0

II I II /?=3v Ë-Í Peptide-C-0-C-C-(Q)—fp)

KUN KCN

crown ether

■

+ R n if \\

N=C-Ç-C-^^© X ^90%

VI.A.17-13 V. J. Hornby, D. A. Upson, and N. S. Agarwal, J. Org. Chem., 42, 3552 (1977). Comparative use o f benzhydrylamine and chloromethylated resins i n s o l i d - p h a s e synthesis o f carboxamide terminal peptides.

405

ORGANIC SYNTHESIS-1977

VI.A.17-14 J . M. S c h l a t t e r , R. H. Mazur, and 0. Goodmonson, Tetrahedron L e t t . , 2851 (1977); D. A. Jones, J r . , Tetrahedron L e t t . , 2853 (1977). ^ . Peptide—(P)

H Pd(0Ac) ? — — DMF

Peptide-OAc

VI.A.17-15 A. E. V a s i l ' e v e t a ] ^ , J . Gen. Chem. (USSR), 47, 1500 and 1505 (1977). — Synthesis of amino a c i d d e r i v a t i v e s of dextran u s i n g : a.

the cyanogen bromide method

b.

a c t i v a t e d esters of carboxydextran and t h e i r aminolysis w i t h s a l t s of amino acids

VI.A.17-16 Yu V. M i t i n and M. P. Zapevalova, Russ. Chem. Rev., 46, 449 (1977). Review:

VI.A.18-1

"Methods o f Synthesis o f Peptides"

P. F. H u d r l i k , J . Am. Chem. S o c , 99., 1993 (1977)

yy

1 . HX

SiMe.

R = n-Pr, n-Hex

2

*

BF

3*

E

t20

X = Br, OAc, OMe

R 62-90%

Reversed stereochemistry can be obtained in some cases.

406

ORGANIC SYNTHESIS-1977

VI.A.18-2 J. Cousseau and L. Gouin, J. Chem. Soc., Perkin I, 1797 (1977).

Θ

Θ

Et 3 NH HC1 2

R-CzC-R'

R1

Cl R = Ph, CH 2 C1, COOMe

^50-90%

R'= H, Me, t-Bu, COOMe

VI.A.18-3

S. Uemura et al., J. Chem. S o c , Perkin I, 676 (1977),

R-C=C-R'

CuCl 2 -LiCl

/

MeCN

CV

R'

^40-90%

R = a l k y l , Ph R'= H, a l k y l , Ph

c=c \

vCuCl2-I2

MeCN

Rx

CT'

/ R

·

c=c

+

c=c \

^70-100%

VI.A.18-4 H. Westmijze, J . M e i j e r , and P. Vermeer, Rec Chim. Pays-Bas, 96_, 168 (1977). 1.

[RCuBr]MgX, THF

2.

NBS, NCS,

c=c

R'-C=CH or

Trav.

I2

>90%

R' = H, alkyl, Ph R = alkyl

Y

407

= Cl, Br, I

ORGANIC SYNTHESIS-1977 VI.A.18-5 A. B. Levy, P. T a l l e y , and J . A. Dunford, Tetrahedron L e t t . , 3545 (1977). R \

Cu-MgBr2 / N-Bromosuccinimide C=C + / \ (or N-Chlorosuccinimide) R' H

R \

yBr(CV

/ C-C

/ R'

\ H

R = n-alkyl R' = H, Ph, n - a l k y l

VI.A.18-6

52-98%

W. G. Salmond, Tetrahedron L e t t . , 1239 (1977).

R-CHO

+

(Me 2 N) 3 P=CCl 2

>-

RCH=CC12

R = a l k y l , Ph, s t e r o i d a l

VI.A.18-7

85-94%

P. Johncock, S y n t h e s i s , 551 (1977). Ph.P

F9CC1-CFC1-R ά

y

EtOH

F9C=CF-R ά

98%

VI.A.18-8 (1977).

R. B. Miller and G. McGarvey, Synth. Commun., 7_9 475 1. X^, CH^Clp

ri-BuCH=CHSiMe3

ά

ά

n-BuCH=CHX

2. Alumina, pentane

X = C l , Br

62-75% i s o l a t e d

408

USEFUL SYNTHETIC PREPARATIONS VI.A.18-9

S. Raucher, Tetrahedron Lett., 3909 (1977). 1 . PhSeBr, CH3CN

R' Br

2. 0 3 , CC14 R-C-CH=CH.

I I R-C-C=CH,

3. A,i-Pr 2 NH

R'

I

L

R' 65-87%

H

ÐÇ,ÂÃ

\ R'=H R' SePh PhSeBr, CC14

H

*-

R-C-CHCH2Br R'

2°2

R,R7H

R = H, n - a l k y l , Ph, i - P r

2

/

c=c /

\

R H 67-87% H / R—C—C

^Br

R' H 51-58%

R'= H, Me, Et

VI.A.18-10 C. Earnshaw, C. J . W a l l i s , and S. Warren, J . Chem. S o c , Chem. Commun., 314 (1977).

0

1. P h 2 P — (

II R

R"x^0Me

LDA OMe, -*

1

R

R,R' = H, Me,

2. NaH, THF

Et, Ar

Y

R^^-R' %60-80%

R" = H, Me

409

ORGANIC SYNTHESIS-1977 VI.A.18-11 G. A. Gareev and Yu. Nl. Belousov, J . Qrg. Chem. (USSR), 1 3 , 606 (1977). 0 CH2=CH0CCH3 ROH

CH2=CH0R

H g + + , H+

R = haloalkyl

"up to 45-50%"

VI.A.18-12 G. M. Rubottom, R. C. M o t t , and D. S. Krueger, Synth. Commun., ]_9 327 (1977). OTMS Z n , C1TMS TMEDA, R = Me, P h ,

VI.A.18-13 L e t t . , 2671

Et20

cycloalkyl

H. S a k u r a i , (1977).

51-85%

K. M y o s h i , and Y. N a k a d a i r a ,

0

Tetrahedron

0SiMe 2 Ph Co(C0)8 +

PhMe 2 SiH

50°, pyridine

85%

410

USEFUL SYNTHETIC PREPARATIONS

VI.A.18-14/VI.A.19-1 936 (1977).

F. Akiyama, B u l l . Chem. Soc. Japan, 5Ç), —

MeCH(SEt)2 or EtSH A l C l o , benzene

SEt 42-81%

VI.A.19-2

K.A.M. Walker, Tetrahedron L e t t . , 4475 (1977).

0 R-OH

Bu3P

+

R-S-R'

N-SR'

i

%90%

0 R = benzyl, c h o l e s t e r y l , etc. R'= Ph, £-ClPh

VI.A.19-3 M. M. Screttas and C. G. S c r e t t a s , J . Org. Chem., 42_, 1462 (1977). ~~ HC104 R-O-R'

+

PhSH

or TFA ->

RSPh

R· = H, Me

R

Widely varying yields.

= alkyl, benzyl

411

ORGANIC SYNTHESIS-1977

VI.A.19-4 E. H. G o l d , V. Chem., 4 2 , 554 ( 1 9 7 7 ) .

P i o t r o w s k i , and B. Z. Weiner, J . O r g .

yx

MeOH

RS È

NO.

RS

ci

^90% R = 1°,2° alkyl, Ph

VI.A.19-5 (1977).

Z=H, CFJ

N. M. Kolbina e t a l ^ , J . O r g . Chem. (USSR), U, —

Ph-C-Br

I

+

Ph-C-S-Ph

BrMgSPh

R'

R1 R,R'

1678

= H, Me, E t , Ph

41-93%

VI.A.19-6 G. H. Posner and M. J . C h a p d e l a i n e , T e t r a h e d r o n 3227 ( 1 9 7 7 ) .

Lett.,

SR

SR RSH A1203

CC13CH0 ''''OH

0

A 1 2 0 3 , CC1 4

29-75%

R = E t , Ph

412

USEFUL SYNTHETIC PREPARATIONS VI.A.19-7 C. T. Goralski and G. A. Burk, J . Org. Chem., 42, 3094 (1977). = Ö

È

BzNEt. B r u

ArSH + NaOH + BrCH2Cl

-

Ar = substituted benzenes, heterocycles

VI.A.19-8

y

ArSCH2Cl ^60-90%

T. Takamoto et aj_^, Synthesis, 884 (1977). Br

Br-(CH29) n-CH-CH29CH20Ph

(QH 2 ) n 2. NaOH

^-S y

CHCH9CH9Ph 2 2

40-74% n = 1-7

Me

VI.A.19-9 K. C. Mattes and 0. L. Chapman, J. Org. Chem., 42_, 1814 (1977). —

CH 3 C0 2 (CH 2 ) 10 Br

Na 2 S 2 0 3 C C

G È > CH 3 C0 2 (CH 2 ) 1 ( ) SS0 3 Na

RS® RSSR

CH 3 C0 2 (CH 2 ) 1 Q SSR 89%, R = Me 93%, R = Et

413

ORGANIC SYNTHESIS-1977 VI.A.19-10 P. G. Gassman e t a j ^ , J . Qrg. Chem., 42, 3233 and 3236 (1977). —

►R (CH2)^

"R'

1 . L i , NH 3 (1), t^-BuOH 2. CH~SSCHQ 3

3

(CH2)^R· H

R,R' = H, Me, a l k y l

v40-60%

n = 3, 4 , 5

CH-S 0

0

1. NaNH 2 , NH 3 (1)

RCH2CNR'R"

2. CH 3 SSCH 3

3

>

I II

RCHCNR'R

R = alkyl

40-60%

R',R" = Me, Ph

VI.A.19-11 (1977). R-X

I . Degani, R. F o c h i , and M. S a n t i , Synthesis, 873

+

,©w K

<=>}>-(

È ß ) — 0-t-Bu

phasetransfer cat.

R-SH

'sv

60-91%

R = 1°,2° a l k y l , Bz X = Br, Cl

VI.A.19-12 E. Vedejs, D. A. Engler, and M. J . M u l l i n s , J . Qrg. Chem., 42, 3109 (1977). R-OH

TfOTf

R-OTf

pyridine

R=al l y 1 i c , propargy 1 ic,ï^-carbony I

414

^40-80%

USEFUL SYNTHETIC PREPARATIONS W. S c h r o t h e t a l ^ , Z . Chem., 17., 411 ( 1 9 7 7 ) .

VI.A.19-13

0 1I.. U-b-L-UMe Cl-S-C-OMe

/p^\

,J^y

J—\

2 . KOH, H 9 0

WJ*$J/

X = a l k y l , a l k o x y l , Br,

SH

80-98%

fused aromatic

VI.A.19-14 133 (1977).

1.

K. Hojo, H. Yoshino, and T. Mukaiyama, Chem. L e t t . ,

fSïl

OTs, Et~N

F-V

CH 3

R -OH

y

0

* || R -S-C-CH3

LiAlH, =V

R -SH

2 . CH 3 C0SH, Et 3 N 79-93% R = a l k y l , benzyl

VI.A.19-15 437 (1977).

ROH

+

>95%

Proceeds w i t h i n v e r s i o n of configuration.

K. Hojo, H. Yoshino, and T. Mukaiyama, Chem. L e t t . ,

(M.

K F

| Ä Me w OTs

Et

3N'

CHC1

= II 2. NaSCNMe.

3

y

||

RSCNMeo

LiAlH,

=U

RSH

^60-97% R = a l k y l , benzyl, cholestanol, p r o t e c t e d sugar, e t c . v

y

415

-

(Inversion

of configuration)

ORGANIC SYNTHESIS-1977

VI.A.19-16

K. H o r i k i , S y n t h . Commun., 7., 251

(1977).

\

■ 00. \

R-COOH 2.

° DCC

R-C-SR'

OH ^80-90%

R'SH, Et 3 N

VI.A.19-17 Y. Yokoyama, T. Shioiri, and S. Yamada, Chem. Pharm. Bull., 25, 2423 (1977).

RCOOH

+ R'SH

DEPC or DPPA y

0 || R-C-SR'

Et 3 N, DMF ^50-90% R,R' = alkyl, aryl, benzyl, etc. DEPC = Diethyl Phosphorocyanidate; DPPA = Diphenyl Phosphorazidate VI.A.19-18

H.-J. Q

G a i s , Angew. Chem. I n t .

1 . carbonyl

|| R-C-OH

E d . , ]6>

di-imidazole y

|| R-C-SR'

R'SH

R = alkyl, Ph, thioester, etc. R'= Et, Ph , i-Pr, t-Bu

416

(1977).

Q


244

>80%

USEFUL SYNTHETIC PREPARATIONS VI.A.19-19 (1977).

A. Pelter et a l ^ , J. Chem. Soc, Perkin I , 1672 0 || R-C-SEt

B(SEt), ^

R-COOH

R = 1°,2°,3° alkyl, Ph

VI.A.19-20 (1977).

^70-80%

D. H. Lucast and J. Wemple, Tetrahedron Lett., 1103

0 II ucn Me,SiCH9CCl -^^

0 || Me,SiCH9CSR

1. LDA, -78° 2. R'R-CO -78°+25°

♦

R = 2°,3° alkyl, Bz

R' H \ / )—Ç / \C.S || 0

R

49-77%

R',R"= H, Ph, i-Pr, cyclic

VI.A. 19-21

T. Takamoto e t a L , J. Qrg. Chem., 4_|,

RX

>-

2180

RSH

2 . " OH, H 2 0 ^60% o v e r a l l

R = Bz, 1°,2° a l k y l , containing ketones, ethers, esters

417

(1977)·

ORGANIC SYNTHESIS-1977 VI.A.19-22 (1977).

R. D. Howells and J . D. McCown, Chem. Rev., 77.* 69 — Review:

" T r i f l u o r o m e t h a n e s u l f o n i c Acid and Derivatives"

VI.A.19-23 J . B. Hendrickson, D. D. Sternbach, and K. W. B a i r , Accounts Chem. Res., 10., 306 (1977). Review:

VI.A.19-24

" T r i f y l A c t i v a t i o n i n Organic Synthesis"

C. S. Rao e t aL_9 Indian J . Chem.,14B, 999 (1976)

Et

H

C / \ R X

3N"P4S10

CH-CN or CHά9 C1ά9 ό

R = Me, subst. Ph

||

 R

/

C

^50-70%

X = NHR', NR' 2 , Rh

VI.A.19-25

\ X

M. Hojo e t a l ^ , S y n t h e s i s , 789 (1977).

0 Il Ar-S-CH2C1

RMgBr

Ar = Ph, £-MePh

R = E t , j_-Pr

418

■

0 || Ar-S-R

55-99%

USEFUL SYNTHETIC PREPARATIONS VI.A.19-26

P. Messinger and H. Grève, S y n t h e s i s , 259 (1977). H0CH2S02~Na®

È

R-CH2NMe3

y

R-CHg-SOg-CHg-R

R = a wide range o f f u n c t i o n a l groups

19-66%

VI.A.19-27 J . B. Hendrickson and K. W. B a i r , J . Org. Chem., 42_, 3875 (1977). — (CF~S0 9 ) 9 0 ό

RLi

ά

ά

or PhN(S0 9 CFj 9 ά ό > E t 2 0 , -78°

R = 1 ° , 2° a l k y l

RS0.CF. ^60-90%

S02CF3 (CF 3 S0 2 ) 2 0 s R

-

>_

A1C1Q 3

R = alkyl (Incompatible w i t h R = 0CH 3 , C l , or N02)

VI.A.19-28

^60-70%

P. D. Magnus, Tetrahedron, 33, 2019 (1977).

Review:

"Recent Developments i n Sulfone Chemistry"

419

ORGANIC SYNTHESIS-1977 VI.A.19-29

A. van der Gen e t a l ^ , Tetrahedron L e t t . , 885 (1977).

Γ~ s 1°°

0 ||

(

f

R

^~~S

)=P(0Et)2

Q

S—*

)·

R'

R,R' = H, a l k y l , a r y l , vinyl, cyclic

VI.A.19-30

K

^70-90%

D.P.N. S a t c h e l l , Chem. Soc. Rev., 6., 345 (1977).

Review:

"Metal-ion-promoted Reactions o f Organo-sulphur Compounds"

VI.A.19-31 409 (1977).

T. L. G i l c h r i s t and C. J . Moody, Chem. Rev., 77, —

Review:

"The Chemistry o f S u l f i l i m i n e s "

VLB.1-1 P. Boontanonda and R. G r i g g , J . Chem. Soc., Chem. Commun., 583 (1977). 0 Λ

PdCl 2 -CuCl 2

R 65-82% R = H, CN, CH2NHC0Me

420

USEFUL SYNTHETIC PREPARATIONS

VLB.1-2 (1977).

B. M. Trost et a L , J . Am. Chem. S o c , 99_, 3088 —

S0C1, pyr, reflux

94%

VLB.1-3 B. M. Trost and P. H. Scudder, J . Am. Chem. S o c , 99_, 7601 (1977). —

0 1. PhSeNa, EtOH y

2. MCPBA, pyridine -70°+-30° 48-85% (stereochemistry may be con­ trolled)

VLB.1-4 H.J.J. Loozen, J. W. de Haan, and H. M. Buck, J. Qrg. Chem., 42, 418 (1977).

H (ÇH2)n

Br

AgOTs

Br

CH3CN

H 62-83%

n = 5-7

421

ORGANIC SYNTHESIS-1977 VI.A.1-5

A. E. Greene et al., Tetrahedron Lett., 2365 (1977) Ov

NR

\ .

CH 2 N 2 , MeOH

H 2 0 2 , HOAc

A1 2 0 3 , CH 2 C1 2 0 =

Ο^Λ

H 95%

0 = =

SR'

\ 1

^^S^.

50%

80%

VLB.1-6 (1977).

E. C. Taylor and C.-S. Chiang, Tetrahedron Lett., 1827

CHR

OMe OMe H o 0®

TTN (CH 2 ) n

CH3OH

2'n

(from W i t t i g reactions) 81-96% n = 1,2,3 R = H, Me, Et

422

Γ

I (CH2'n 9)

USEFUL SYNTHETIC PREPARATIONS

VLB.1-7 R. P e l l i c c i a r i and B. N a t a l i n i , J . Chem. Soc., Perkin I, 1822 (1977).

0

COOEt

ethyl diazo(lithio)acetate

OH

^

33%

VLB.1-8

W. Schroth and W. Kaufmann, Z. Chem., ]]_, 331 (1977). R

{X<

1.

:CC1.

2. NaOEt, EtOH, rfx.

^60% (second step)

R = H, Ph

VLB.1-9 P.F.S. Filho and U. Schuchardt, Angew. Chem. Int. Ed., 16, 647 (1977). c' R2-C-CH2-C-R3

+ Ph

0

0

R' = H, Me, Ph

JT^i

i

H generally 50-100%

R2 = Me, Et, Ñ ú é , ºcyclic R3 = Me, Ph,

Ni(acac) 2

Ph

J

423

ORGANIC SYNTHESIS-1977

VLB.2-1

Y. Ohfune e t a L _ , T e t r a h e d r o n L e t t . ,

279 ( 1 9 7 7 ) .

Br AgOAc AcOH, 120c

^

57%

VLB.2-2 (1977).

D.H.R. Barton et al., J. Chem. S o c , Perkin I, 1107 0',È

© S ^ S

v

COOEt

1.

Ctf

h v , MeOH

2. Bu3P

OMe

C0

2Et

9% Many a d d i t i o n a l

VLB.2-3 (1977).

N. Minami and I .

Kuwajima, T e t r a h e d r o n L e t t . ,

.0 1.

0

+

LiOCH(TMS) 2 CH CHMe ^, , n c

RI.C-H

r

2. 3.

HC1 CH 2 N 2

R = H, Me R1=

Ph, a l k y l ,

2

R

N

/ /

H

MeOOC

OC

\j

51-85% vinyl

424

examples

1423

USEFUL SYNTHETIC PREPARATIONS

VLB.2-4 J. J. Eisch and K. R. Im, J. Organomet. Chem., 139, C51 (1977).

S

^

^

E ^^

2(C0D)9NiBipy THF, 50°

E

^

E = 0, NH, S

50-70%

W. Pfeiffer, E. Dilk, and E. Bulka, Synthesis, 196

VLB.2-5 (1977).

Ph

^

V

;

N.

.. „

,N

ñç^^Í/ê

_..

NaOEt, EtOH

-

| R'

H

ph

" " ^ Ë

y\^

Ph

R = H, Me, a l l y l , Ph, e t c .

nr I

%80-90%

R'= H, Me

VI.C.1-1

M. E. Jung e t ajh_, J . Org. Chem., 4 2 , 3961 (1977).

I 3 R-C=CHCH2R'

I . PruC ^~ßÃÏ

"

R,R' = a l k y l , cyclic

|| R-C-CH=CHR'

49-85% for cyclic cases 23-45% for acyclic cases

425

ORGANIC SYNTHESIS-1977

VI.C.1-2 (1977).

B. M. Trost and G. Lunn, J . Am. Chem. S o c , 99_, 7079 —

Me S

-° *

a

/

0 COOMe

/

\ ^5.

VI.C.1-3 M. E. Jung and J. P. Hudspeth, J. Am. Chem. S o c , 9£, 5508 (1977). — MeO

MeO v

OMe

.OMe

1. Δ

R'

2. Na, NH 3 , EtOH 1. KMn04,

R,R* = cyclic, alkyl,

buffer

H, Ph, COOMe

2. H 3 0 ®

HOOC

R'

H20

22-40% o v e r a l l

426

Vr

COOH

USEFUL SYNTHETIC PREPARATIONS

VI.C.l-4 (1977).

W. G. Dauben and D. M. Michno, J. Org. Chem., 42, 682 —

pyridinium chlorochromate

R = Me,Bu,Ph

0 31-98%

81-96%

VI.C.1-5 (1977).

R

T. Takeda, M. Ueda, and T. Mukaiyama, Chem. Lett., 245

*^\

o

J$ R],R2

= al K y i ,

0

X

1- EtOOCNNCOOEt, KpCO,

'

T~Q— 2. ^ Ï Ç

Ë R

|l

D2

NNHCOOEt aryl 1.

NaBH,

2.

HC1, AcOH-H 2 0

OH

0 õ50-60%

427

ORGANIC SYNTHESIS-1977

VI.C.1-6 (1977).

E. McDonald and R. T . M a r t i n , T e t r a h e d r o n

,N0.

NO, A r ' C H O , HC(0Me) 3

1. NaBH 4

Ar'

MeNH 3 Cl, KOAc, MeOH

Ar

L e t t . , 1317

2. TiCl 3 ,

Ar

NaOH

65-77%

Ar,Ar' = _ ^ Q V _ OR

ÁÃ'^ã'

OR'

^65%

VI.C.1-7 (1977).

R. G. Carlson and W. W. Cox, J . Org. Chem., 4 2 , 2382 —

OH C=CH <^

1.

LICECH

CECH

P0Cl 3 -Pyr y

THF

(CH^

2. MCPBA

^CHjpn

n = 0-7 1.

L i , NH3(1)

2.

CrOo

ÏÎÏÇ

[CH y 2 n

428

USEFUL SYNTHETIC PREPARATIONS

VI.C.1-8 D. Seebach, M. S. Hoekstra, and G. Protschuk, Angew. Chem. I n t . E d . , 1 6 , 321 (1977). 0

y

ci

NO. LDA 1. 2 LDA 2. THF/H20

^20-60% o v e r a l l

VI.C.1-9

M. Montury and J . Gore, Tetrahedron L e t t . , 219 (1977).

Ö Tl(0Ac)3

-v flAc

3o

y OAc 1. BH2. CH3C00H R

429

OAc

ORGANIC SYNTHESIS-1977 VI.C.1-10 J . L . C . Kachinski and R. G. Salomon, Tetrahedron L e t t . , 3235 (1977).

PhCOCHN. IT

v_0H

BF3-Et20

R = methyl, cyclic / o r

Ph(Me)

r=r

"o ^80-90%

NaH>

OMe CH2Br. TMSC1, Et3N/DMF

0.

.Ph(Me)

SiMe3 HIO,

Ph(Me)

MeOH %90%

^70-90%

VI.C.2-1 C. A. Bunnell and P. L. Fuchs, J. Am. Chem. Soc, 99_, — 5185 (1977). NNHTs

Jv^COOMe \cH2)n

1. 3 LDA

<

2. -78°->RT 3. RX

n = 1-3 RX = Mel, BzBr

430

f^f~

COOMe

\cH2)n ^50-80%

USEFUL SYNTHETIC PREPARATIONS VI.C.2-2 (1977).

Cl-

S. Terashima and S. Jew, Tetrahedron L e t t . , 1005

.C

(X

R·

C00H

Q*.

C00H R1

o-

H ^ R

«

H^^R

CV

C00H

o-

•OH

.R'i

'

CH2R

c=o

R1

CH2R

VI.C.2-3 R. M. Scarborough, J r . and A. B. Smith I I I , Tetrahedron L e t t . , 4361 (1977); D. L i o t t a and H. Santiesteban, Tetrahedron L e t t . , 4369 (1977).

0^

NaSePh

(CH 2'n

v>

SePh

(CH 2 ) n

1. CH2N2 2. -PhSeH

n = 1-8

OCH 3

(CH

J

2}n

60-70%

431

ORGANIC SYNTHESIS-1977 VI.C.2-4

D. S. Watt et a l ^ , J . Am. Chem. S o c , 99_, 182 (1977). 0

CN

(EtO)2PCH.

\ /

R'

O-t-Bu

C=0 NaH

R

CN

R'

O-t-Bu

R,R' = H, a l k y l , Ph, c y c l o a l k y l

ZnCl, Ac 2 0

R

CN

R'

OAc

X

V

COOH

R1

OR"

57-88%

V

R'

COOR"

60-95%

432

NHR"

V

CONR"

R1

81-100%