Angewandte Chemie International Edition: 1992Sep 26, 2020 · Alex Rerick Angewandte Chemie...

Angewandte Chemie International Edition: 1992Alex Rerick Baran Group Meeting09/26/2020

1

1992 Nobel Prize in Chemistry awarded to Rudolph Marcus for his theories on

electron transfer

Riots begin in LA over the brutalization

of Rodney King

Jay Leno becomes host of The Tonight

Show

Jeffrey Dahmer sentenced to life in

prison

Mall of America opens in

Minnesota

Cartoon Network, first animated TV channel, is

launched

January

February

March

April

May

June

July

August

September

October

November

December

John Gotti sentenced to life in prison

Bill Clinton nominated for

president

Silence of the Lambs wins best picture at

the Academy Awards

Quincentenary of Columbus’ voyage to the Americas

Designated as the International Space Year by the United Nations

Slovenia and Croatia gain

independence

Bill Clinton wins presidency

Princess Diana and Princes Charles

separate

Shen Tong arrested for Tiananmen

Square protests

Scientific Advancements in 1992

• Discovery of the first exoplanet• Richard Dawkins delivers “Viruses of the Mind” speech• ViolaWWW is released by Unix• IBM Simon, the first smartphone, is released• The first text message is sent • Edmond Fischer and Edwin Krebs win the Nobel Prize in Medicine for their advancements in elucidating the function of reversible phosphorylation

Top Cited Articles

1. The Organosulfur Chemistry of the Genus Allium: Implicatioms for the Organic Chemistry of Sulfur. Block, E., 1135 (870 Citations)

2. Control and Design Principles in Biological Mineralization. Addadi, L.; Weiner, S. 153 (731 Citations)

3. Electron Localization in Solid-State Structures of the Elements - The Diamond Structure. Savin, A. et al., 187 (678 Citations)

4. Synthetic Bilayer-Membranes - Molecular Design, Self Organization, and Application. Kunitake, T., 709 (607 Citations)

ACIEE in 1992442 articles

Most Prolific Authors

1. Hans Pritzkow (7 publications)2. Paul von Ragué Schleyer (7 publications)3. Francois Diederich (6 publications)4. Horst Kessler (6 publications)5. Klaus Müllen (6 publications)


2

New Anticancer AgentKern, W. et al., 64

Me O

O

Me12 O

N(CH3)3I

Me O

O

Me12 O

N(CH3)3I

Me O

O

Me12 O

N(CH3)2

Me O

O

Me12 O

N(CH3)2

+

+

OH

Me12 O

N(CH3)2

a. PCCb. Ac2O, K2CO3

Me12 O NaO

N(CH3)2+

Isothiocyanate-Substituted Allenes and 1,3-ButadienesBanert, K. et al., 90

R1SCN

R2

H

R2

R1

NCSN

S

N

S

HN

S

HN

S

X Me

Me

Me

Me

S

O

PhO

HX

PhOHNaOH

H2S

H2O, NaOHgas-phase

thermolysis

R = H or Me

Nucleophilic Attack at the Central Carbon Atom of (π-Allyl)Palladium ComplexesHoffmann, H.M.R. et al., 234

CO2Me

TMEDA, CO

CO2Me

Me

[Pd]

PdCl

X = OMe, NH2, NHPh, NPh2, SCHMe2

R1

[3,3]

[3,3]40-50 oC

R2

NCS

R1

R3

R3

NCS

R1R1 = Me or HR2 = Br, Cl R2 = SCN

R3 = CN, CO2Me

Me

X

Me

X[3,3]

NCS

Me

SCN

Me

NCS

NCS

MeMe

and (Z, E) + (E, Z)X = OTsX = SCN

MeI

Me

Me

Me

Me O

OBnMe

O

OBnMe

Me

N

n(H2C)DCN, hv

C N CH

n(H2C)C N C

H

n(H2C)

NR

Pr

NR

Pr

N

N

PrR

n(H2C)

DCNHN

CO2MeMeO2C

n(H2C)N

n(H2C)DCN, hv

C C CO2MeMeO2C

N

N

conditionsNN

CO2MeMeO2C

CO2MeMeO2C

[3+2] Cycloaddition with Azaallenyl Radical Cations Müller, F.; Mattay, J., 209

PdCl

TMEDA, CO[Pd]

[3,3]

R3 R3

CN

CN

DCN


3

R = D, CH3RR R

Anti-Bredt Enol Ethers by Transannular CyclizationDetert, H. et al., 791

HOO

OOHO+

HO O O+

An Organometallic “Criss-Cross” CycloadditionKelley, C. et al., 1053

N NM

Cp

COCO

MCp

OCOC

Ph

PhRe C CH2Cp

OCCO

Mn C CH3Cp

OCCO

+

CN

NC

Ph

H

H

Ph

or

NH

N

CO2MeMeO2CMe

NH

N

CO2MeMeO2CMe

H

NH

N

CO2MeMeO2C

H

H

HNH

N

MeO2C

H

H

H

OMecoryantheine

180 oC

Pictet-SpenglerTFA SnCl4

NH

N

MeO2C

H

H

HLiI 3 H2O

Benzene as a Dienophile in an Intramolecular [4+2]Grimme W. et al., 872

Tandem Sakurai-Carbonyl-Ene Reaction for Steroid SynthesisTietze, L.F.; Rischer, M., 1221

Me

H H

Ot-Bu

Me

HO

H

Me Ot-Bu

Me

Me

H

Ot-Bu

Me

OSiMe3

O

Me Ot-Bu

O

MeO2C

H

TMS-OTf

EtAlCl2 gave access to β-OH at C-7 and β-Me at C-6

Me

H H

Ot-Bu

Me

Me

HO

H(PPh3)3RhCl

180 oC

180 oC

double [3+2]H2

Diastereoselective Entry to Coryanthe Type Indole Alkaloids by Intramolecular Ene ReactionTietze, L. et al., 1079


4

Pd-Catalyzed C-H Activation of Methoxy GroupsDyker, G., 1023

Pd-Catalyzed Intermolecular AdditionsTrost, B.M. et al., 1335

Atom economical redox methodChemoselective

Affords (E)-isomers selectively

R

OR1

OAc(dba)3Pd2•CHCl3, PPh3 R

OR1OAc

OAc

Pd-Catalyzed Three Component Coupling of Allyl Benzoates, Zincioesters, and COTamaru, Y. et al., 645

Me OCOPhIZn CO2Et

HMPACO+ + Me

OCO2Et

Enantioselective Syntheses of Cyclopentanoid CompoundsBaldenius, K.U. et al., 305

MeMe

N

NR

R

FeCl2

R = (1R)-menthyl

Me

Me

MeMe

+

[Fe]

Me

Me

RO

R = Ac, CHO, Me, Et

Me Me

OSit-BuMe2

OAc

MeO

O

OH

MeO

O

Me

O

OOH

O

Me

OSit-BuMe2

OAc

MeO

O

Me

O

OO

O

Me

OSit-BuMe2

OAcTDMPP =

Tris(2,6-dimethoxyphenyl)phosphine

O OO

+Pd(OAc)2

Pd(PPh3)4

Me

Me

BF3 • Et2O

AcO

AcROH

BF3 • Et2OAc2O

Me

Me

Me

Me

Me

+ +

Me

[Pd]

HOAc

TDMPP

IO

MeO

MeO

Pd(OAc)2K2CO3, n-Bu4NBr

100 oC

MeO

PdO

MeO

O PdIO

Pd

OMe

PdI

OMe

OMeO

MeO

PdI


5

Br

BrBr

Br

BrBr

R

R

R

R

R

R

R

Synthesis of HexabutadiynylbenzenesVollhardt. K.P.C. et al., 1643

Synthesis of TetraalkynylmethanesBunz, U. et al., 1648

Enantioselective Grignard AdditionsWeber, B.; Seebach, D., 84

RMgBr (3 equiv.)a. TADDOL (1 equiv.)

b. O

R2R1

R2

R OH

R1

O

O

Ar ArOH

OH

Ar Ar

TADDOL

Ligand Effects in Grignard AdditionsReetz, M.T. et al., 342

MgL2

better selectivity for aldehydes than RMgX provides

O

MePh

O

HPh+ RMgL

Ph OH

R

RLi RMgL

O OH

Ph

Ph

OHPhMgL

diasteroselectivity for equatorial Ph, up to 95:5 dr

+

Diastereoselective Route to β-Stannyl and β-Silyl AlcoholsLautens, M. et al., 232

Me

OH

SnBu3

R

Me

OH SnBu3

R

Me

OH

SiMe2Ph

R

Me

OH SiMe2Ph

R

(dppb)Rh(nbd)BF4

One-Pot Synthesis of Ketones from Carbon Dioxide and OrganolithiumsZadel, G.; Breitmaier, E., 1035

CO

O R1Li R1 COLi

O

R2Li R1 COLi

OLiR1 C

O

R2

(dppb)Rh(nbd)BF4

+

Br2

NaNH2

KNH2

CuI, Et3N

R = H, t-Bu3, Sit-Bu3

MeOH

MeOH

THFEt2OTADDOLEtMgBr

PhCHOPhCHO

No β-elimination side products

L = bulky sulfonyls

H2O R2Li

R2

R1 COH

R2R2

RBr

Br

RBr

Br

PdCl2(PPh3)2

R = H

R = MeR = HR = Me

t-Bu t-Bu t-Bu

H2

H2


6

CHO

Me Me

CHO

Me Me

Me Me

Me MeOH

OH

Me Me

Me MeOH

OH

Ten Membered Ring EnediynesNicolaou, K.C. et al., 1044

Me Me

Me MeO

O

Me Me

MeMe

O

O

Swern

+

OOH

Me Me

HOO

Me Me

+

OOH

Me Me

OOH

Me Me

Me Me

MeMe

X

X

Me Me

MeMe

X

X

Butadiene-Tricarbonyliron Complexes to Access (E, E)-DienylallenesNunn, K. et al., 224

CHOMeO2C MeO2CFe

OHH

R1

MeO2CH

EtR

R1

Et

MeO2C

Diastereoselective Michael Addition of β-Ketoesters to Prostereogenic α,β-Unsaturated Carbonyl CompoundsOuvrard, N. et al., 1651

Me R2

O+

MeOCO2R1

CO2R1R2

OO

Me Me

MeO

CO2R1R2

O

Me

Enantioselective Synthesis of 3-Substituted 2-KetoestersEnders, D. et al., 618

MeO

OAr

O

SAMP MeN

OAr

O

N

OMe

MeN

OAr

O

N

OMe

a. t-BuOK, n-BuLi MeO

OAr

OR

R1Li

a. ClCO3Phb. (EtCuBr)MgBr • LiCl

(NH4)2Ce(NO3)6

R

BF3 • Et2OH2Ob. RX

Phosphoenolpyruvate (PEP)

OH

O

OPO32

de = 85-95 %

+

R = Me, t-Bu, Bz R = Me, H

K2CO3, Δor

Cs2CO3crown ether

diastereofacial control1 2 Me

O

EMe

H

Me

O

EH

Me

R2 O

O

R2

1 2

105 oC

50 oC

d-toluene

100 oC

hv, O2

Review on Enediyne Anticancer Antibiotics: Nicolaou, K.C.; Dai, W.M. Angew. Chem. 1991, 30, 1387For Biological Mode of Action: Jerić, I.; Gredičak, M. Acta Pharmacol. Sin. 2007, 57, 133

Fe

Fe

D

D

(CO)3 (CO)3

(CO)3

SmI2


7

OMe

R2OOMe

OR2

O

IMe

OMeOMe

S

OO

OR2

OMeN

O

OR2

Me R1

O O

OMeN

Me

HNO

HMe

CO2H

OMe

O

OOH

OH OH

H

NO

H

O

O

OSO

O

Calichaemicin-Dynemicin Hybrid MoleculesNicolaou, K.C. et al., 340

NHCO2MeO

MeSSS

O

R1 =

Calicheamicin

Dynemicin

OMe

HOOMe

OH

O

IMe

OMeOMe

S

OO

OH

OMeNH

O

OH

Me R1

O O

OMeHN

Me

OMe

TESOOMe

OTES

O

IMe

OMeOMe

S

OO

OTES

OMeN

O

OTES

Me X

O O

OMeN

Me

YFMOC

R3

1: X =2: X = OH, Y = H3: X = H, Y =

O NO2

OCCl3NH

a. hvb. CCl3CNc. 8

4: R2 = TES, R3 = FMOC5: R2 = H, R3 = FMOC6: R2 = R3 = Hd. HF, py

e. Et2NH-THF f. NaBH3CN

ab

de

Early Studies of Dynemicin: (a) Schreiber, S. L. et al., J. Am. Chem. Soc. 1990, 112, 7410. (b) Schreiber, S. L. et al., J. Am. Chem. Soc. 1992, 114, 5898.Total Syntheses of Dynemicin: Myers, A. G. et al. J. Chem. Biol. 1995, 2, 33Danishevsky, S. J. et al., J. Am. Chem. Soc. 1996, 118, 9509Calchaemicin Oligiosaccharide Core: Nicolaou, K.C. et al., J. Am. Chem. Soc. 1990, 112, 8193Total Synthesis of Calichaemicin γ: Nicolaou, K.C. et al., J. Am. Chem. Soc. 1992, 114, 10082

7, when R1 =

7

A

B

C

D

4

8


8

Total Synthesis of the Carbohydrate Fragments of Esperamicin ANicolaou, K.C.; Clark, D., 855

O

O

O

HO

SSSMe

O O

OH

MeO

OMeO

MeO NH

OOMe

HN O O

OH

SMeMe

MeO

O NOMe Me

MeH

Esperamicin A

Fragment 2

Fragment 1

o-Nitrosobenzylated Fragment 2

O ON

O

Me

OTBS

Me

OTESO O

OMeNFMOC

Me

Me

O

NO2

O

OMe

OHO O

OMeNFMOC

Me

Me

O

NO2

O OMe

OTBSO

NH2

OCl

O ON

O

Me

OH

Me

OHO O

OMeN

i-Pr

FMOCO

NO2

MeS

OMe

OH

O

NO2

OO

O

OF

OMeNFMOC

Me

Me+

+

a. AgClO3, SnCl2b. NaH, ethylene glycolc. nBu2SnO then nBu3SnOMe, Br2

a. pTSA

a. TCDIb. toluene, 100 oC

pdtb. Et2NH

b. Et3SiOTfc. iBu2AIHO OMeMe

HO OHOH

a. CDI

b. TCDI

O OMeMe

OOO

O

Im

SO SPhMe

HOOH

O SPhMe

TESOO

O

NPhthMeO

MeOpdt

COOH

NH2MeO

MeOCOCl

NPhthMeO

MeO

a. nBu3SnH, AIBNb. PhSSiMe3, ZnI2

nBu4NI

b. coupling 1. pthaloyl chloride

a. hydrazine

OMeO

Cl

2. (COCl)2

c. NaHethylene glycol

b.

c. Et3SiOTf

a. nBu2SnO

O ON

O

Me

OTBS

Me

OTESO O

OMeN

i-Pr

FMOCO

NO2

S

a. NaSMe, EtSHb. MeI, DiPEA

OH

Silylated Fragment 1

a. NaBH3CN, BF3•OEt2N

O

N

c. AcOH, nBu4NFthen K-selectrided. HF•py


9

Total Synthesis of (±)-Mitomycin KDanishefsky, S.J. et al., 915

N N Me

O

O

MeO

Me

OMe

mitomycin K

OMeMeO

MeOMe

NO2

OH OMe

N

OMe

OMe

OMeO

Me

OMehv a. PDCb. PhSCH2N3 N

OMe

OMe

OMeO

Me

OMe

NN

N

SPh

O

a. L-Selectride

b. TCDI N

OMe

OMe

OMeO

Me

OMe

NN

N

SPh

S

N N Me

O

O

MeO

Me

OMeOH

TMS

N N Me

OMeMeO

Me

OMeOH

TMS

OMe

AgII

N N Me

OMeMeO

Me

OMe

OMe

TMSMeLiO

a. Bu3SnH, AIBNb. hvc. Raney Ni

N

N

Me

N N

N

N

Me

N N

366 nm

>412 nm

OOBr Br

O

BrCO2

Br

Photostimulated “On-Off” Guest BindingWillner, I. et al., 1243

Enantioselective Synthesis of RolipramMulzer, J. et al. 870

BnO

MeONO2

NO

O

Me

O

Bn

Previous Total Syntheses of Mitomycins: (a) Kishi, Y. et al., J. Am. Chem. Soc.1977, 99, 8115 (b) Fukuyama, T. et al., Tetrahedron Lett. 1977, 4295

N

ONO2

OBn

OMeO

Bn

O

a. NaHMDS

b.

O

OMeHN

O

Rolipram

OH

OMeHN

OH2, Raney NiBr

NaH

HO

N

N

S

pyridinep-toluenesulfonate

NaOAC

Angewandte Chemie International Edition: 1992Sep 26, 2020 · Alex Rerick Angewandte Chemie...

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Transcript of Angewandte Chemie International Edition: 1992Sep 26, 2020 · Alex Rerick Angewandte Chemie...