baran group meeting eros: vol i and iibaran group meeting eros: vol i and ii will gutekunst...

Will GutekunstBaran Group MeetingAluminum Bromide

OHi-Pr

O

i-Pr

Cl

AlBr3, hv

DCM, rt

Oi-Pr

AlX2

67%

JOC (56) 5745

Me

Me

AlBr3, tBuBr

50 -60C, 1h65%

"sludge catalyst"

Me BEt

Et

BrAlBr3

CCl4, RT95%

Me BBr

Et

Et

Chem Comm (1972) 71

Aluminum Hydride

Nn

n = 1-4

AlH3

70-92% nH

Tetrahedron (24) 4489

Acetylmethylenetriphenylphosphorane

N

O140C

Ph3PMe

O

N

O Me

Chem. Ber. (114) 3146

Ph3PMe

O

R N3

R = Ts, Bz, Ar (slow)R = Alkyl, no reaction DCM

NN

NR

Me

Ph3PMe

O

DCMR N

ClHN

Ar

NArN

Me

R

JOC (31) 1587; JOC (37) 3213

Alumina

35C, 2 h85%

I2 activatedalumina

I Bu H

Bu

I

I

H

JOC (53) 4477

HXalumina (or silica)

DCM

H

HX

JACS (115) 3071HX can be generated in situ by TMSX, (COX)2, SOCl2, etc.

Aluminum

MeN

NMe

N

NO

OEtO

Al(HgCl2)

aq MeOH-NH381%

MeN

NMe

O

O NH

NMe

Heterocycles (24) 1565

Lumazine to pterin

Ammonium Peroxydisulfate

Me

Me

O

Me

Na2S2O8NaCN, H2O

80C, 68%

Me

Me

O

MeCN

Tet Lett, (27) 4215

EROS: Vol I and II

Will GutekunstBaran Group Meeting EROS: Vol I and II

Ammonium Sulfide

Me

O

CONH2

(NH4)2S

dioxane/H2O

CONH2

(NH4)S

dioxane/H2O

CO2H

O O

H

O O

NH2

MeO

NH2

(NH4)S

dioxane/H2O26%

(NH4)S

dioxane/H2O20%

O

NH2

(NH4)S

dioxane/H2O60%

Cl Also converts alcohols, thiols, amines and alkynes into primary amides

Baker's Yeast

MeCO2Me

Me

MeMeO

Me

MeMe

ultrasonicallystimulated

baker's yeast

31%, 96% eeHO

Me Me

Me

Me

MeH

Me

Me

CO2Me

(racemic)

O

H OGlu

MeO2C

OO

O

H

MeO2C

OO

O

O

MeO2C

OO

OH OH

baker's yeastpH 7.5

baker's yeastpH 6.4

JACS (110) 604

Chem Comm (1991) 825

Benzene Sulfonyl Azide

NMe

PhSO2N3ether

71% NMe

NSO2Ph O

PhSO2N3MeCN

reflux O NSO2Ph NSO2Ph

O

J. Het. Chem (24) 1413 JOC (31) 2847

Benzene Sulfonyl Bromide

NH

PhN

Ph

Br3.5 eq PhSO2Br

THF, aq NaOHBu4NOH

quantitative SO2Ph

JCS Perkin 1 (1983) 2417

Benzene Sulfonyl Isocyanate

R

X

Y

PhSO2NCO

R

NSO2Ph

Y

XNSO2PhR

Y

O-COX

30-71%

X = S, OY = alkyl, aryl, O, NR2, S, CO2R

R1

R2

X

Y

R1,R2 = H, alkyl, arlX,Y = H, OR; O; S

PhSO2NCO R1R2

XY

NSO2PhO

Benzenetellurinic Anhydride

Me10 mol%

[p-EtOC6H4Te(O)]2O

reflux AcOH85%

Me

Me

O

Bis(acetonitrile)chloronitropalladium(II)

C8H17

Pd(MeCN)2(NO2)2O2

C8H17 C8H17

NO2 O

Toluene 11:1Acetone 1:7Only terminal olefins, long reaction

times, stoichiometric in Pd

Tet Lett (27) 6099

Organometallics (3) 1479

180C

0.1 mm


Bis(allyl)di-µ-chlorodipalladium

O OMe

H1. LDA, THF2. Pd allyldimer

TEA or HMPA 78%

PdCl

ClPd

OOMe

Me

H

MeMe

JOC (45) 5193

Bis[N,N-bis(trimethylsilyl)amino]tin(II)

I Sn[N(TMS)2]2

PhHSn

(TMS)2N N(TMS)2

I

JCS Chem Comm (1978) 192

Bis(cyclopentadienyl)mehylzirconium Tetraphenylborate-Tetrahydrofuran

NMe H NMeMe

Rcat. Cp2Zr(Me)BPh4

H2

JACS (111) 778

Bis(dimethylglyoximato)(methyl)-(pyridine)cobalt(III)

NCo

NO

Me

Me

N Me

Me

OH

py

Me

O OH

Me

MeO

MeOH

Me

MeOH

MeOH

MeOH

MeOH

CoI(dmgH)2

80%

hv

PhH94%

CoX

Tet Lett (32) 243

Bis(pyridine)iodonium(I) Tetrafluoroborate

Me MeF

I

N NIBF4

-

2 HBF4, DCM-60C, 30 min

78% JOC (56) 2234

Bis[N-(p-toluenesulfonyl)]selenodiimide

Seo

DCMTsN

Cl

NaTsN Se NTs

MeMe

TsN Se NTs

82% MeMe

NHTsOTMS

Me

TsN Se NTs

51%

OTMS

Me

TsHN

MeMe

TsN Se NTs

51%Me

Me

NHTs

JACS (98) 269

Bis[N-(p-toluenesulfonyl)]sulfodiimide

Me TsN Se NTs MeSeNTs

NTs Me TsN Se NTs Me

Me Me

NHTsNHTs

68%

Prepared from SeOCl2 Prepared from chloramine-T

PhTsN S NTs Ph

NTsTsHNS

Na2SO3

DME94%

Ph

NHTsPhH, 10C

91%

Ph

NTsTsHNS

PhH

reflux

Liebigs Ann Chem (1975) 1725

TsN S NTs

PhH, RT75%

Cl ClSNTs

NTs

Tet Lett (1966) 1671

Me MeMe

MeO

HTsN Te NTs

PhMe, reflux100%

Me MeMe

MeNTs

H

JOC (56) 6468

R

Will GutekunstBaran Group Meeting EROS: Vol I and IIBis(trimethylsilyl) Peroxide-Vanadyl Bis(acetylacetonate)

Me

OH Me

Me

OH

Me

Me

Me

OH

OH

Me

OH OH

MeMe

Me

Me

Me OH

Me

O

30 mol% (TMSO)210 mol % VO(acac)2

DCM, rt, 5h85%

30 min

70%

4h

81%

Me

Me

OH OH

MeMe

7h

68%

10 min

80%

TL (24) 3741Borane–Pyridine

NBH3

- Mild reducing agent with greater hydrolytic stability than NaBH4 in protic solvents and higher solubility in aprotic organic solvents.- Inexpensive and less toxic alternative to NaCNBH3 for reductive aminations

TBDMSO

1. 1 eq Py-BH3 0.5 eq I2, RT

2. NaOH, H2O2 83%

TBDMSOOH

JACS (127) 5766Borane–Tetrahydrofuran

1-hexene

2-hexene

3-hexene

HB; 150C, 16h

HB; 150C, 16h

HB; 150C, 16h

Me BR2

MeMe

BR2

MeMe

BR2

92%

5%

3% JACS (88) 1433

Me BH3, thendiglyme, 160C

4 h, 67%

HO

JACS (89) 561

Me

Me

B3

Br2

hv Me

Me

B2

Me

MeBr H2O

86%

MeMeMe

MeB

OHMe

Me

1. Br2, H2O hv

2. [o] 46%

MeMeMe

MeMe

MeOH

JACS (93) 1025

Boric Acid

R

O O

OEt

O

OEt

B(OH)3170C, 1.5h

80%

R

O

O

OEt

NH

PhCO2H

0.3 eq B(OH)3reflux mesitlyene

82%

+1.1 eq N

O

Ph

Boron Trichloride

NHMe MeNBCl3

TEA, PhHBCl2

NHMe

OH

Ar

NHMe

O

R

ArCHO

RCN

Formylation with isocyanides. Similar ortho selectivity observed with phenols. JACS (100) 4842

Boron Trifluoride

2-fluoropropaneBF3

82%

Me

Me BF3

20C, 4h94%

BrF Br

JACS (64) 1032 J Chem Soc (1957) 2174

MeOAc

Me

MeMe Me

O

BF3(g)wet DCM

RT, 10 min90%

All other conditions/LA's failed

camphor

Ph

ClF2N

Me

NF

BF3

DCM68%

Ph

ClF2N

F

J Chem Soc Perkin 1 (1973) 2109

Will GutekunstBaran Group Meeting EROS: Vol I and IIBoron Trifluoride–Acetic Acid

Bu3Sn OH

Ph

Me

PhBF3•2AcOH

97%

Ph

Me

Ph

Tet Lett (24) 4591

Boron Trifluoride Etherate

C5H11

O

5CO2Me

C5H11

O

5CO2Me

BF3•OEt2

PhH35% mix of cis and trans

Chem Comm (1967) 984Bromine

Br

Br

Br2

Coll. Czech. Chem. Comm (27) 1927

Bromine–t-Butylamine

OH OHBrBr MeO MeO

OHBr

OHBr2 (2 eq)t-BuNH2 (4 eq)

Tol/DCM-70C to rt

75%

Br2 (1 eq)t-BuNH2 (1 eq)

Tol/DCM-70C to rt

87%JOC (32) 2358; JOC (58) 3877

Bromine–Silver(I) Oxide

MeMe OH

Me MeO

Me

Br2, Ag2Opentane

rt, dark75%

Br2, Ag2O

rt, pentane"one ethereal

product"

Me

MeMe OH

EtOMe

Me

MeEt

JACS (86) 3905; Tetrahedron (40) 2643

4-Bromobenzenesulfonyl Azide

OTMS 4-BrPhSO2N3MeCN

73%

NSO2Ar

OTMS

OMe 4-BrPhSO2N3MeCN, 63C

83%

NSO2Ar

OMeMe

Me Me

Me

Tet Lett (27) 4701

Bromomagnesium Diisopropylamide

O

Me

Me

Me TMSCl

Et2OTEA, HMPA

95%

(iPr)2N MgBr TMSO

Me

Me

Me

TMSO

Me

Me

Me

97:3

+

Bromomagnesium Hexamethyldisilazide

Otherwise, very similar to bromomagnesium diisopropylamide

Me

Me

O

OMe

BrMgN(TMS)2

Tol, 0C80% Me

Me

O

OMe

Mg Br

N(TMS)2

Coll. Czech. Chem. Comm. (38) 3499

Bromomethanesulfonyl Bromide

S

S

S Br2

H2OBr S

Br

O O RR

BrS Br

O O

hv, -15C RS Br

O OTEA

Br SBr

O O

hv, -15C

KOtBu53%

Me Br SBr

O O

hv, -15C

KOtBu65%

Ph Ph85% 81%

B(OR)2 B(OR)2

Bromo(o-tolyl)bis(triethylphosphine)-nickel(II)JACS (108) 4568

Me

NiBr

PEt3

Et3P

MeO I

3 mol% catBu4NBr, PhH

80C, 68%MeO Br

Br Cl3 mol% cat

Bu4NCl, PhH

80C, 88% Br Cl

3 mol% catBu4NCl, PhH

80C, 96%

JOC (45) 1930


Bromotrimethylsilane

Me

CO2H

TMSBrDMSO, iPrNEt2

CHCl3, RT85%

OO

Br

Me

(most yields 40-60%)Heterocycles (31) 987

cis halolactonization

t-Butyllithium

II

t-BuLi

94%

n-Butylnitrite

Me

HN

C5H11

BuONO

92%Me

C5H11

JACS (110) 7230

Tet Lett (1969) 4001

MeMe

MeMe

MeMe

NN

OO nitrosodimer

BuONO, PhSiH310 mol% Fe(acac)3

PrOH, 73%

Carbon DioxideOM

CO2

OH OH

+

M = Na (150C, 80% yield) 97:3M = K (210C, 48% yield) 4:96

Chem Lett (1992) 1137

Carbon DisulfideO CS2, MeOLi;

MeI

46%

O

S

SMe

OMe

Chem Lett (1982) 123

Carbon Monoxide

OOSiEt2Me

OSiEt2MeO

OMe

OSiEt2Me

OMe

OSiEt2MeHSiEt2Me, CO4 mol% Co2(CO)8

RT, PhH, 20h88%

HSiEt2Me, CO4 mol% Co2(CO)8

RT, PhH, 20h81%

JACS (111) 7938

R NH2

R = butyl, hexyl, octyl, cyclohexyl

CO (1 atm)cat. Seo

THF, RT95-99%

NH

O

NH

RR

JACS (93) 6344

(s-Bu)3B

1 atm. COdiglyme

125Cthen H2O2

87%

(s-Bu)3COH

Cesium Fluoride

O

H

MeCsF, MeCN

77%

N

S S TMSS

Me

Tet Lett (33) 85

Chloramine-T

Me

SO2NClNa

Me

MeN

Chloramine-TDCM, RT

77% Me Me

O

H

N

R1

R2OR R1

R2

ONHTs

Chloro(cyclopentadienyl)dimethyltitanium

NH2

Ph

CpTiMe2Cl

THF, RT

N

Ph

TiCpCl N

Ph

TiCpCl

NPh

R1

NH

R2

O

iPr

96%

81%

H2O

iPrCN

(catalytic with CpTiCl3) JACS (114) 5459

BnOO

CO (41 atm)5 mol% Co2(CO)8

10% 3-hydroxypyridine

60C, MeOH86%

BnOOH

CO2Me

JOC (64) 2164

CO2H

CO2H


Chlorodimethylsilane

PhMe

NH2

BuLiClSiMe2H Ph

Me

NHMe2Si SiMe2H

0.2 mol %Pt[(CH2=CH)Me2Si]2O2

RTN SiMe2

Ph iPr

HMe2Si

PhiPr

OH

NH2

H2O2KF

76% overall

RMe

OSiMe2H

Pt cat. RMe

O SiMe2

PhMe

NHMe2Si SiMe2H

PhMe

HMe2SiN SiMe2

Rh cat.

JOC (55) 3438Similar chemistry with chlorodiisopropylsilane and chlorodiphenylsilane

2-Chloroethyl Chloromethyl Ether

Bn

ClO Cl

LiTMP

0C to RT34% Bn

O Cl BuLiTHF/Hex/HMPT

rt, 1 h

80%

OH

Bn

trans:cis = 99:1

JACS (103) 2443C-(1-Chloroethyl) N-Cyclohexyl Nitrone

Me

NCyO

Cl AgBF4DCE

Me

Me NCy O

Me

Me

Me

K2CO3, 0C;PhH 80C

95%N

Cy

O

Me

Me

MeNcy O

Me

Helv Chimica Acta (55) 2187

NCy O

Me

Me

H

KCN NCy O

Me

Me

HNC

tBuOK

80C>90%

Me

H

OCyN

Helv Chimica Acta (55) 21981-Chloroethyltrimethylsilane

MeOH

H

Me O Cl

Me

TMS

sBuLi, THF

-78C to RT40%

(yields generally higher)MeO

H

H

Me O

MeOH

H

MeMe

TMS

O Me

H+

93%

Organometallics (1) 893

3-Chloro-1-hydroxytetrabutyldistannoxane

SnO

SnOHCl

Bu BuBuBu

SnY Sn

OOSn

SnY

R R RRR

RR RX

X"extremely stable in air and to moisture and thus can be handled and stored in the open air. Because this compound is not volatile, it is virtually nontoxic under the usual conditions."

O

OR1 HOR2

O

OR2 H2OR1+ +

cat.

O

OH2 HOR2

O

ORH2O+ +

cat.

Usually, catalyst loadings are below 1 mol% (some examples at even 0.05 mol%).Also catalyzes acetal formation/deprotection and THP/silyl deprotection.

Chloromethyllithium

R BO

O MeMe

MeMe

Cl I

BuLi-78C

RB

O

O MeMe

MeMe

Cl rt BO

O MeMe

MeMe

R

Organometallics (4) 1687R = Me, 93%R = vinyl, 90%

1-Chloro-1-nitrosocyclohexane

NOH

hypochlorite

95%

N OCl

OAc

OAc

EtOH87%

H2N

O

Cl

OAc

OAc

N-Chlorosuccinimide

NMe

NCS

THF89%

NCS

CHCl3NaHCO3

76%

NMe

N

O

O

NMe

Cl

Chlorosulfonic AcidTet Lett (29) 2405

Liebigs Ann Chem (1981) 610

OO

O

Ph

ClSO3H

55% OO

O

PhO

OO

Ph

JACS (105) 2414

OEtEtO

+


Chlorosulfonyl Isocyanate

R

O

OH

R = tBu, Cy, ClCH2CH2, Bn, PhCH=CH, 1-naphthyl

ClS

O O

NOSO3 + ClCN

130C

Nu

} cycloaddition

CSIR

O

O

O

NH

SO2Cl-CO2

R

O

NH

SO2ClDMF

RCN

Ph

O

H

CSIPh

O O

N SO2Cl PhO O

N SO2ClO

Ph

PhN

SO2Cl> 0C

< 0C

XX = O, NH, S

1. CSI

2. DMF XX = O, NH, S

CN

O

NCHN

Me

Ph 1. CSI

2. H2O, OH-

O

N

Me

PhOHN

O

R1R2

HO CN

CSIR1

R2

ONH

O

O

R2

R1O R3

R4

R2R1 R3R4

+O O

R2R1 R3R4

O NSO2Cl

NSO2Cl O

major

CSI

PhH/DCM-10C

10 min

Me

MeMe

1. CSI

2. H2O, OH-

43%

Me

MeMe

NH

O

STol

RHgCl

STol

RHgCl

CN1. CSI

2. DMF

Et EtCSI

DCM, 0C95%

NO2S O

Et Et

Cl

Et Et

ClO2SNO

JOC (37) 196

Et Et

O

Et Et

HN CO2MeSO3Me

H2O, HCO3-

MeOH,MeO-

Chlorosulfonyl Isocyanate (cont.)

OBnCSI, Na2CO3

DCM, RT

90%NH

NHCbz

Cbz

+

8.4:1

MeCSI, Na2CO3

DCM, RT

72%NH

CBzOBnMe

Me

NHCbz

+

1:1CSI, Na2CO3DCM, -78C

82%%

Me OBn

MeNH

CBzMe

Me

Tet Lett (41) 5073

Chlorotrimethylsilane

Me

Me

R

O

Me

Me

R

OTMSCl, NaI

MeCN

95%

TMSCl, NaIMeCN

94%

Tet Lett (22) 3551

Chlorotris(triphenylphosphine)rhodium(I)

MeMeMe

O

H

5% RhCl(PPh3)31 eq DPPA

THF, RT90%

MeMeMe

Me

only primary aldehydes

ClRhPh3P

PPh3

CO DPPACl

RhPh3PPPh3

L

+

PPhO

PhOO

NCO

Chromium(II) Acetate

JOC (57) 5075

O

O

HO

MeI

O

O

HO

MeH

Me

H

HO

O

Me

Br

HOMeMe O

O

Cr(OAc)2EtSH

DMSO

Cr(OAc)2BuSH

DMSO80%

(5 eq Cr and 7.5 BuSH)JOC (17) 290Can also use CrCl3 with Zn(0)


Cobalt(II) Acetate

O O

OMe

1-hexene (2 eq)Co(OAc)2

O2, AcOH60C, 68%

OMe

HO C4H9

MeO2C


Copper(II) Acetate

10 eq

tBuOOHCu(OAc)2

AcOH, 60C74%

Tet Lett (34) 567

Copper(II) Acetate–Iron(II) Sulfate

OMe

MeO

OH

OMe

MeO O

O3

89%

O

OOH

O

OMe

O

O

OMe

Cu(OAc)2Fe(OAc)2

MeOH, RT83%

JACS (107) 2980

O

Me

MeO

Me1. O3, MeOH2. Cu(OAc)2

Fe(OAc)2 76%

O3, MeOH;Cu(OAc)2

Fe(OAc)267%

Me

OMe

Me

O

O

OO O

H Me

H Cu(OAc)2Fe(OAc)2

O

O

Me

H

O

O

H

Copper(I) Iodide–Triethylphosphine–Lithium Naphthalenide

OBr

OHOHCuI, Bu3PLiNp

Toluene (45%) 1:0THF (56%) 1:6 Tetrahedron (45) 443

Copper(I) Phenoxide

4 PhOCu + CS2MeCN, RT

92% PhO

OPh

OPhOPh

Cyanogen Azide

N3CN

16-18C96%

NCNMe

Me

Me

Me

O

1. N3CN, LiClO4 MeOH

2. HCl, MeOH 60%

JACS (91) 3676

(1,5-Cyclooctadiene)(1,3,5-cyclooctatriene)ruthenium

MeMe

Me

MeMe

Me

Me

1 mol% Ru(cod)(cot)Et3SiH

80C, 2h59%5 eq

Me

Me SiEt3

Me

Me SiEt3

Me

Me SiEt3

same

61%

same

39%

Cyclopropyldiphenylsulfonium Tetrafluoroborate

CO2MeSPh2

BF4

KOH, DMSO83%

CO2Me

SPh2

BF4

KOH, DMSO96%Me

Me

O

O

MeMe

O

OHBF4

96%Me

MeO

O

O Me

TolLiN

Hexane, RTca quant

LDA OH

Tol

OH

MeTol

Cyclopropyltriphenylphosphonium Bromide

N

O

O

PPh3

Br

68% N

O

OH

R1

OCO2Et

R2

PPh3Br

CO2Et

NaH88-95%

R1 CO2EtR2

EtO2C

JACS (96) 1607

Will GutekunstBaran Group Meeting EROS: Vol I and II(Diacetoxyiodo)benzene

Ph2 eq PIDA

4 eq TMSN3

DCM, 61%

Ph

O

CNMe

Me

Me

CNMe

Me

Me

O

2 eq PIDA4 eq TMSN3

DCM, 65%


HNHN

RO

PIDA

MeOH, -23C60%

RMeO2C

R = Me, CO2Me, CH2CO2Me, Ph, etc

1,2-Diaminoethane

HNHN

MeO

PIDA

MeOH, -23C57-66%

MeO2C

R = Me, Et, CH2CO2Me, BnH R

R

H

H


OI

I

H

H

Greatly increases the ability of Cr(II) to reduce alkyl halides, aryl halide and epoxides.

Cr(II)en10% aq DMF

RT, 92%no benzyne

Cr(II)en10% aq DMF

RT, quant

C15H31

LiHNNH2

reflux in DAE

2h, 90%


C15H31Me

cis:trans 2:3

R (CH2)n Me

R = butyl, pentyl, octyln = 2,3

Li, DAE10-15C

PhH/Hexane

5 min71-76%

H (CH2)n+1 R

Dianisyl Telluroxide

Me OHO OO

TeO

OMeMeO10 mol%

Tol, reflux96%

TeO

OMeMeO

NC CN Te

OMeMeO

CNNC

Tet Lett (22) 5251

1,4-Diazabicyclo[2.2.2]octane

EtPh

PhO

Br

1. DABCO, BuLi PhSMe2. NaI, MeI, DMF

80C, 24h 92%

EtPh

PhO I

DABCO forms stable, crystalline complex with organometallic complexes with Li, Zn and Mg organometallicsAlso promotes lithiation of toluene, benzene, etc.

"Haller Bauer Cleavage"

MeO

O

OMe

DABCONaNH2

PhH, reflux76% MeO

O

NH2

SO O

MeMeMe

S

Cl Cl

MeO O

DABCODMSO, RT

90%

Synthesis (1975) 395

Diazomethane

CH2N2

HBF4

HOH

H H

Me

HMe

C8H17

MeOH

H H

Me

HMe

C8H17

O

OH

MeO

H OH

Me

OH OH

R

OH

Me Me

H

Me

HMe

O OH

O

OH

MeO

H OH

Me

OH OMe

R

OH

Me Me

H

Me

HMe

O OMe

CH2N2

JACS (110) 2506

Me CO2Cl

1. CH2N2

2. HClO4

MeO

J. Chem. Soc. Perkin 1 (1981) 1203

Will GutekunstBaran Group Meeting EROS: Vol I and IIDiazomethane (cont.)

Me Me

OSO2Cl

Me Me

O

Et3NCH2N2

TMS O

OMe

O

OMe

TMSCH2N2

Journal of Organometallic Chemistry (52) C7

baran group meeting eros: vol i and iibaran group meeting eros: vol i and ii will gutekunst...

Documents