R.A. Rodriguez EROS: vol III and IV

R.A. Rodriguez

EROS: vol III and IV

Dibenzoyl Peroxide (DBP)

+

O

O

tBu DBP cat.

O

80 ?C, 24h

67%

O Ph Ph O

O

O tBu O

O OtBu

Di-t-butyl Azodicarboxylate

O

DBAD

80 ?C, 24h

O

67%

MeO

Ph N O

DBAD 86%

O

N O N Boc

Boc BocHN Boc

N Ph

Synlett 1989, 30

MeO

N O

Chem Ber 1991, 124, 2279

Me

CO2Me +

Dibromoalane

O tBu O

O

DBP cat.

80 ?C, 24h 62% Me

O O

CO2Me

Org. Synth. Coll. Vol. 1973, 5, 93 Tet 1985, 41, 4047

Me O

Me O

Me Me

MeAl(OR)2

O

Br2AlH

82%

selective for more hindered

Me Me OH

Dibromomethane-Zinc-Titanium (IV) Chloride

JACS 1988, 110, 2650

MeO2C Me

CH2Br2 Zn, THF

O

TiCl4/DCM rt, 15min

Me THF, rt, 24h 94%

MeO2C Me

JOC 1980, 45, 2005 Me

O

O

ON

Bn

1. LDA 2. DBAD

63% Br

Di-t-butyldichlorosilane

tBu

tBu Si tBu

tBu Si

+

Me

Me

O

HO N

Boc N Boc

TL 1992, 33, 7613

tBu

tBu

tBu Si Si tBu

+

Me

Me

Me

tBu tBu Si tBu Si tBu H

Di-t-butyl peroxide (DTBP)

O

NMe2 O

H

NMe2

O N CH2 Me

Me

DTBP

N

NMe2

1:2 (A:B) 90%

A

O

Me

CHO

TBHP/FeII

exclusive A;

N

N Me

57%

B

Gazz. Chim. Ital. 1973, 103, 13

R.A. Rodriguez

EROS: vol III and IV

Di-n-butyltin Oxide

HO BnO

OH O

BnO OBn

1. i. DBTO (1.1 eq) PhH, reflux

ii. remove solvent

2. Br2, DCM, Bu3SnOMe 87%

O BnO

OH O

BnO OBn

JCS(P1) 1979, 1568

Dicarbonyl(cyclopentadienyl)[(dimethylsulfonium)methyl]iron Tetrafluoroborate

Me

Fe

CO2Me

OC CO

SMe2 BF4

86% H

Me CO2Me

H

TL 1982, 23, 1871

1,2 Dichloroethylene

O R

VO(OEt)Cl2 O2, EtOH

R = OEt, 64% R = Me, 52%

O VO(OEt)Cl2 CuCl2, Et2O 43%

O VO(OEt)Cl2 CuCl2, Et2O R CN

Dichlorobis(triphenylphosphine)-nickel (II)

Dichloroketene O

MeMgBr NiCl2(PPh3)2

O

96%

OH Me

SOPh

Cl Cl 72%

O R

Bull. Chem. Soc. Jap. CO2Et 1989, 62, 2399

Cl

CO2Et

JOC 1991, 56, 2264

R NC Cl

CO2Et

R = H, 55% R = Me, 55%

SPh O

O

Cl H Cl

JACS 1981, 103, 7687

PhMgBr NiCl2(PPh3)2

O

64%

Ph

Dichloroborane Diethyl Etherate

N3 + BCl2

92%

OH JOC 1985, 50, 719

H N

JACS 1973, 95, 2394 T 1987, 43, 4079

H Cl Cl HO

1.Zn/HOAc 2. H2O2

1. Zn/HOAc 2. NH2OH 3. PPA

1. Zn/HOAc 2. NH2OH 3. P2O5,

MeOSO2H

H

O H H

O 90%

N HH H

O 53%

NH HO

94%

R.A. Rodriguez

EROS: vol III and IV

N,N-Dichlorourethane

O

Bu

Cl2N OEt Bu

NCHO2Et

PhH, 40 ?C

Cl

65%

Dichloromethyllithium

OO

Me O B

O

LiCHCl2 O O ZnCl2

-100 ?C

Me

OO

OBn O B O

Et

H2O2 79%

1. LiCHCl2 ZnCl2 -100 ?C

2. EtMgBr -78 - 20 ?C

82% (2 steps)

180 ?C 80%

Bu NH

O

O

KOH, EtOH 50 ?C, 4h Bu

70%

NH

JOC 1966, 31, 3625 JOC 1968, 33, 766

Cl O

B O Me

LiOCH2Ph

94% (2 steps)

OO

OBn O

B O Me

N,N-Diethylaminodimethylsilane

HSiMe2NEt2 Ni(acac)2 1 mol % DIBAL (2 mol%) PhH, 50 ?C, 6h

57%

HO SiMe2NEt2

CO2Et

O Si Me2

CO2Et

Me Ph

OH

HSiMe2NEt2 rt, 2h

Me

Me

Ph

cat Pt[{(CH2=CH)Me2Si}2O]2 Ph

OSiMe2H

rt, 87%

O SiMe2

Organometallics 1993, 12, 2297 JACS 1989, 111, 6478

H2O2

Me

62% Ph

syn:anti = 85:15

OH OH

N,N-Diethylaminosulfur Trifluoride

O S Me Me

DAST, DCM rt

SF Me

OO

OBn OH

O

Me

O

Me JOC 1987, 52, 5116

Et 1,2-Diethoxy-1,2-bis(trimethylsilyloxy)-ethylene

EtO TMSO

OTMs + OEt

O

1. ZnCl2 (7 mol%)

O

DCM, rt 30 min

2. MeOH, HCl

84%

CO2Et

Methoden Org. Chem. 1985, B.E5, 57 O

O S OMe

CO2Et

DAST, SbCl2 DCM

91%

F S

CO2Et

OMe

TL 1988, 29, 5729

JOC 1990, 55, 4757

R.A. Rodriguez

EROS: vol III and IV

Diethyl-t-butoxycarbonyl-methylaluminum

4-Dimethylaminopyridine

Et2AlCH2CO2tBu O

tol. rt, 8h 5%

Me

DME, rt, 4h 45%

OH CO2tBu Me

Synthesis 1983, 284

NNO2

Ac2O DMAP

JOC 1979, 44, 4116

Diethylzinc-Bromoform-Oxygen

OEt

Et2Zn, CHBr3

OTMS O2, 1 min

H

rt, 2h 82%

CO2Et

H OMe Et2Zn, CHBr3

OTMS

O2, 1 min rt, 2h 80%

CO2Et

tBu

OMe

Et2Zn, CHBr3

H

OTMS

O2, 1 min rt, 2h 40%

Dilithioacetate

TMS OLi

O

OLi

84%

tBu

CO2Me

JACS 1984, 106, 7283

CO2H

Chem Comm 1975, 537

Dimethyl Acetylenedicarboxylate

O-

Cl

N+

EtO2C

CO2Et

Cl

100 ?C

N

EtO2C N N

CO2Et CO2Et JHC 1992, 29, 1001

Dimethylchloromethyleneammonium Chloride

Me

OOH

N+

Me

Me

H

Me

Me

Me

66%

Me

Me O

2,2-Dimethyl-1,3-Dioxane-4,6-Dione

O

Me

O Me Pyrolysis

Me

Me

Me

O

Me

O O

MeS

O Me

625 ?C

Me

O

10-3 Torr

O

Dimethyl Dithiobis(thioformate)

O OH

S

O O

1. 2.2 eq LDA 2. (MeOCS2)2

3. Metal halide 4. RCHO

O O

R+ O

O

R

RCHO Metal Halide

nPrCHO

-

nPrCHO nPrCHO

ZnCl2 CuI

PhCHO

-

PhCHO

CuI

overall Yield 57 58 56 52 51

E:Z 96:4 9:91 7:93 100:0 4:96

TL 1982, 1887

Me Me

Chem Comm 1990, 375

O O

MeO

S

S

R

S

O

O Me S

O Chem lett 1980, 595

R.A. Rodriguez

EROS: vol III and IV

N,N-Dimethylhydrazine Me2NH Me O N PhBr, reflux 38%

Diisobutylaluminum Hydride

N,N'-Dimethylpropyleneurea (DMPU)

Me

N

OH

O HN NEt2

O Me N N Me

DMPU

O HN NEt2

JCS(P1) 1992, 749

H NMe

H

1. 10 eq. tBuLi/THF 2. 10 eq. MeI,

-78 ?C

+ H

NMe Me

O

HN

NEt2

H NMe

Me

DIBAL

92% N

OH

N H

1,3-Dimethyl-2-phenylbenzimidazoline (DMBI)

O Cl DMBI, AIBN 90%

O Me

TL 1983, 24, 4711

DMBI Me NH N Me

Me Me Me

O Me

DMBI, AlCl3 96%

Me Me

O Me

Me

TBDMSN

Cosolvent Yield(%) TBDMSN

A B

A

-

6 73

DMPU 82 10

Dimethyl Sulfoxide-Oxalyl Chloride

OSiEt3 OSiEt3

1. DMSO, (COCl)2 2. Et3N

85%

OSiEt3 O

TBDMSN B

TL 1988, 29, 6429

JACS 1993, 115, 3056

Dimethyl Sulfoxide-Silver Tetrafluoroborate

DMSO, AgBF4

Me

Br

TEA, rt

Me

5

83%

5 CHO

NO2Ts DMBI, DBPO MeCN 99%

Dimethylsulfide

1.i. tBuOCl, -65 ?C NH2 ii. Me2S -65 ?C

iii. NaOMe

90%

NO2

JACS 1991, 113, 8074 Bull. Chem. Soc. Jap 1986, 59, 1747 Me JOC 1988, 53, 3897

Br DMSO, AgBF4

TEA, rt

Me

3

Me

80%

O

3

Me

TL 1974, 917

Dimethylthiocarbamoyl Chloride

NH2

2. Raney Ni

NH2

CH2SMe

88%

Me JACS 1973, 95, 588

S

HCl, rt

N O NMe2

S

95%

N HO

NMe2

O

N

S

NMe2

JOC 1966, 31, 3980

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