Baran Group Meeting JACS: 1987 A Year in Review Dane Holte · Baran Group Meeting JACS: 1987 A Year...

11
Dane Holte Baran Group Meeting JACS: 1987 A Year in Review Overview: 1987, vol. 109 – 8123 pages – ~60 total synthesis papers Publication record: Barry Trost E.J. Corey Leo Paquette Samuel Danishefsky Phil Magnus Clayton Heathcock K.C. Nicolaou Larry Overman Stuart Schreiber K. Barry Sharpless Gilbert Stork Key methodologies developed and/or refined: Stereospecific Cross-Coupling of Vinyl Halides with Vinyl Tin Reagents Catalyzed by Palladium. J.K. Stille and B.L. Groh, 813–817. Palladium-Catalyzed Coupling of Aryl Triflates with Organostannanes. A.M. Echavarren and J.K. Stille, 5478–5486. Highly Enantioselective Borane Reduction of Ketones Catalyzed by Chiral Oxazaborolidines. Mechanism and Synthetic Applications. E.J. Corey, R.K. Bakshi, and S. Shibata, 5551–5553. Asymmetric Hydrogenation of β-Keto Carboxylic Esters. A Practical, Purely Chemical Access to β-Hydroxy Esters in High Enantiomeric Purity. R. Noyori, T. Ohkuma, M. Kitamura, H. Takaya, N. Sayo, H. Kumobayashi, and S. Akutagawa, 5856–5858. A Stable and Easily Prepared Catalyst for the Enantioselective Reduction of Ketones. Applications to Multistep Syntheses. E.J. Corey, R.K. Bakshi, S. Shibata, C-P. Chen, and V.K. Singh, 7925–7926. 13 10 8 7 6 5 5 4 4 4 4 O O O O HN HO MeO H N Et Me O O Me OH S Me I O OMe OMe O OH MeO HO Me O O N H O OMe HO MeSSS H Calichemicins, a Novel Family of Antitumor Antibotics. 1. Chemistry and Partial Structure of Calichemicin γ 1 I . 2. Chemistry and Structure of Calichemicin γ 1 I . M.D. Lee, T.S. Dunne, M.M. Siegel, C.C. Chang, G.O. Morton, and D.B. Borders, 3464–3466 and 3466–3468. Notable Isolation Papers: HO MeO O Me OH O Me O N Me O O O Me OMe H OMe Me Structure of FK506: A Novel Immunosuppressant Isolated from Streptomyces. H. Tanaka, A. Kuroda, H. Marusawa, H. Hatanaka, T. Kino, T. Goto, and M. Hashimoto, 5031–5033. iPr N Me Me NH O N O iPr Me sBu OMe N O OMe Me HN O S N The Isolation and Structure of a Remarkable Marine Animal Antineoplastic Constituent: Dolastatin 10. G.R. Pettit, Y. Kamano, C.L. Herald, A.A. Tuinman, F.E. Boettner, H. Kizu, J.M. Schmidt, L. Baczynskyj, K.B. Tomer, R.J. Bonttems, 6883–6885. structurally related to: Esperamicins, a Novel Class of Potent Antitumor Antibiotics. 2. Structure of Esperamicin X. 3. Structures of Esperamicins A 1 , A 2 , and A 1a . J. Golik, J. Clardy, G. Dubay, G, Groenwold, H. Kawaguchi, M. Konishi, B. Krishnan, H. Ohkuma, K. Saitoh, and T.W. Doyle, 3461–3462 and 3462–3464.

Transcript of Baran Group Meeting JACS: 1987 A Year in Review Dane Holte · Baran Group Meeting JACS: 1987 A Year...

Page 1: Baran Group Meeting JACS: 1987 A Year in Review Dane Holte · Baran Group Meeting JACS: 1987 A Year in Review Dane Holte Overview: 1987, vol. 109 ... H2, Ra-Ni, Et3N 2.Ph CH2 O, AcOH,

Dane HolteBaran Group Meeting JACS: 1987 A Year in Review

Overview: 1987, vol. 109– 8123 pages– ~60 total synthesis papers

Publication record:Barry Trost E.J. Corey Leo Paquette Samuel Danishefsky Phil MagnusClayton Heathcock K.C. Nicolaou Larry Overman Stuart SchreiberK. Barry Sharpless Gilbert Stork

Key methodologies developed and/or refined:

Stereospecific Cross-Coupling of Vinyl Halides with Vinyl Tin ReagentsCatalyzed by Palladium. J.K. Stille and B.L. Groh, 813–817.

Palladium-Catalyzed Coupling of Aryl Triflates with Organostannanes.A.M. Echavarren and J.K. Stille, 5478–5486.

Highly Enantioselective Borane Reduction of Ketones Catalyzed by Chiral Oxazaborolidines. Mechanism and Synthetic Applications. E.J.Corey, R.K. Bakshi, and S. Shibata, 5551–5553.

Asymmetric Hydrogenation of β-Keto Carboxylic Esters. A Practical,Purely Chemical Access to β-Hydroxy Esters in High Enantiomeric Purity. R. Noyori, T. Ohkuma, M. Kitamura, H. Takaya, N. Sayo, H. Kumobayashi, and S. Akutagawa, 5856–5858.

A Stable and Easily Prepared Catalyst for the Enantioselective Reduction of Ketones. Applications to Multistep Syntheses. E.J. Corey,R.K. Bakshi, S. Shibata, C-P. Chen, and V.K. Singh, 7925–7926.

1310876554444

OO

O

O

HNHO

MeO

HNEt

MeOO

Me

OH

S

MeI

OOMe

OMe

O

OHMeOHO

Me

O

O

NH

O

OMeHO

MeSSS

H

Calichemicins, a Novel Family of Antitumor Antibotics.1. Chemistry and Partial Structure of Calichemicin γ1

I.2. Chemistry and Structure of Calichemicin γ1

I.M.D. Lee, T.S. Dunne, M.M. Siegel, C.C. Chang, G.O. Morton,and D.B. Borders, 3464–3466 and 3466–3468.

Notable Isolation Papers:

HO

MeO

O

Me

OH

O

MeON

Me

O O

OMe

OMe

H

OMe

Me

Structure of FK506: A Novel Immunosuppressant Isolated from Streptomyces. H. Tanaka, A. Kuroda, H. Marusawa, H. Hatanaka, T. Kino, T. Goto, and M. Hashimoto, 5031–5033.

iPr NMe

Me

NHO

N

OiPr

MesBu

OMe N

O

OMeMe

HN O

S

N

The Isolation and Structure of a Remarkable Marine Animal Antineoplastic Constituent: Dolastatin 10. G.R. Pettit, Y. Kamano, C.L. Herald, A.A. Tuinman, F.E. Boettner, H. Kizu, J.M. Schmidt, L. Baczynskyj, K.B. Tomer, R.J. Bonttems,6883–6885.

structurally related to:Esperamicins, a Novel Class of Potent Antitumor Antibiotics.2. Structure of Esperamicin X.3. Structures of Esperamicins A1, A2, and A1a.J. Golik, J. Clardy, G. Dubay, G, Groenwold, H. Kawaguchi, M. Konishi, B. Krishnan, H. Ohkuma, K. Saitoh, and T.W. Doyle, 3461–3462 and 3462–3464.

Page 2: Baran Group Meeting JACS: 1987 A Year in Review Dane Holte · Baran Group Meeting JACS: 1987 A Year in Review Dane Holte Overview: 1987, vol. 109 ... H2, Ra-Ni, Et3N 2.Ph CH2 O, AcOH,

Dane HolteBaran Group Meeting JACS: 1987 A Year in Review

Total Synthesis and Absolute Configuration of 7,20-Diisocyanoadociane.E.J. Corey and P.A. Magriotis, 287–289.

OH

Me

MeMe

+O OO

Me O

iPrO O

1. PhSeSiMe3 (1.3 eq), HO(CH2)2OH (xs), I2 (cat.)2. mCPBA3. Me2S, (iPr)2NH

Me O

iPrO OO

Me (CH2)2OTBMSH

PhMe, 150 ºC20 h (90%)

TBMSO(H2C)2 Me

OO

H

O

O

[4+2]

Me

OO

H

BzO

OOOBz

Me

PhMe, 185 ºC36 h (54% + 36% other diaster.)

MeH

MeCN

MeH

NCMe

7,20-Diisocyanoadociane

[4+2]

Syntheses that will be discussed today:

MeH

MeCN

MeH

NCMe

7,20-Diisocyanoadociane

O

O

Me

MeHO

Me

O OH OH

OH

OH OH

OH

CO2H

OAmphotericin B

OH

O

OH NH2

OHMe

HOMe OH

Me

HOOH

Aphidicolin

N

N

MeOMe

HOHCO2Me

OCOMeEt

H

(–)-Vindoline

NN

N

O H

H H H

O

O

MeO

Me Me

CNHO

(±)-Cyanocycline A

NH

AcN

CO2Me

(±)-Clavicipitic Acids

MeOH

H

H

Me

HMe Me(±)-2-Desoxystemodinone

O

OO

MeO

MeOOMe

O

O

(–)-Steganone

Me MeMe

MeMe

H

(±)-Laurenene

Pagodane

N NH

R

MeO

OOMeOCONH2

Mitomycins

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Dane HolteBaran Group Meeting JACS: 1987 A Year in Review

O

O

Me

MeHO

Me

O OH OH

OH

OH OH

OH

CO2H

O

Stereocontrolled Construction of Key Building Blocks for the Total Synthesis of Amphoteronolide B and Amphotericin B. K.C. Nicolaou, R.A. Daines, J. Uenishi, W.S. Li, D.P. Papahatjis, and T.K. Chakraborty, 2205–2208.

Total Synthesis of Amphoteronolide B. K.C. Nicolaou, R.A. Daines, and T.K. Chakraborty, 2208–2210.

Total Synthesis of Amphotericin B. K.C. Nicolaou, R.A. Daines, T.K. Chakraborty, and Y. Ogawa, 2821–2822.

OH

O

OH NH2

OHMe

β-gylcosideformation

macrolactonization

Horner-Wadsworth-Emmons (HWE)

OHO

Me

MeRO

Me

O O O

OR

O O

OR

CO2Me

O

MeO

O (MeO)2PO

HO

HWE HWEacid-induced

THP formation

HWEHWE

OHMe

MeRO

Me

CO2Et

RO

O O

O

O O

O

ORO

BnO

O

(EtO)2PO

O

(MeO)2PO

PhO

OR

OH H

OBnBnO

(+)-diethyltartrate

EtOOEt

O

OH

OH

O

O

HO OH

OHHO

O

HO OH

OHHO

(+)-xylose

(–)-xylose

OBnOH OH OH

OBnOH OH OH

OBnHO

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Dane HolteBaran Group Meeting JACS: 1987 A Year in Review

Stereocontrolled Total Synthesis of (±)-Cyanocycline A. T. Fukuyama,L. Li, A.A. Laird, R.K. Frank, 1587–1589.

NOH

tBuO2C

Me

CO2tBu LDA, THF, -78 ºC;then ZnCl2 (1.5 M);

OMeMe

MeOOBz

H

O

then:OMe

Me

MeOOBz

OH

NCO2tBu

OH

tBuO2C OMeMe

MeOOBz

O

NCO2PG

CO2Me

OH2N H

H

CSA, quinoline,PhH, reflux, (85%)

(77%)

(34% over 10 steps)

MeOMe

MeOOBz

HN

N

H

H

O

then NaBH3CN (64%)mechanism?

MeOMe

MeOOBz

HN

N

H

H

O

NHO

MeOMe

MeOOH

HN

N

H

H

O

NH CO2PG 1. H2, Ra-Ni, Et3N

2. PhCH2OCH2CHO, AcOH, MeOH(66% over 2 steps)

CH2OBz

CO2Me

NOCl, -35 ºC;CO2PG CO2PG

CO2MeCO2Me

(37% over6 steps)

Me

MeOOAc

HN

O

NNCO2PG

AcO

MeOH H H

CN

1. Lawesson's reagent mechanism?

PS

PS Ar

SAr

S

Me

MeOOAc

N

NNCO2PG

AcO

MeOH H H

CN

2. "Careful" Ra-Ni (74% over 2 steps)

Me

MeOOAc

N

NNCO2PG

AcO

MeOH H H

CN

O , MeOH, 60ºC

O

(99%)

NN

N

O H

H H H

O

O

MeO

Me Me

CNHO

(±)-Cyanocycline A

(42% over 4 steps)

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Dane HolteBaran Group Meeting JACS: 1987 A Year in Review

Enatioselective Total Synthesis of Aphidicolin. R.A. Holton, R.M. Kennedy, H-B. Kim, M.E. Kraft, 1597–1600.

TBSOMe

O

Me

1. LDA, PhMe, -78 ºC2.

-78 ºC to r.t.O

STolO

O

3. vinyllithium (7 eq), 1 hr4. HF/MeOH, 20 min5. NaOMe, 0 ºC, 1.5 hr(45% after chromatography)

O

S(O)TolO

OMe

Me

TBSOMe

OMe

Me

O

Me

O

S(O)TolO

Me

Me

O

Me

O

S(O)Tol

HOMe OH

Me

HOOH

with vigorNH

NMeO

Et

OFirst 5 steps can be done in one-pot, before lunch: MeO2C

Me

HO

tBuOCl; then DBU (3 eq),0 ºC, 20 min

(75% with one recycle)

N

N

MeOMe

H OHCO2Me

OCOMeEt

H

(–)-VindolineN

N

MeO

OEt

H

CO2Me

mechanism?

Synthesis of (–)-Vindoline. P.L. Feldman and H. Rapoport, 1603–1604.

Total Synthesis of (±)-2-Desoxystemodinone. A Novel Hydroxyl-Assisted, Intramolecular Ene Reaction. J.D. White and T.C Somers, 4424–4426.

CHOOH

Me

Me

HMe Me

PhMe, 110 ºC16 h (94%)

MeOH

H

H

Me

HMe Me

H

OH

Me

HMe Me

OH

OH

"The pivotal role of the hydroxyl substituent in this process was verfied by its reductive removal..."

(Title withheld for your own good). P.J. Wagner and K. Nahm, 4404–4405.(Title withheld for your own good). P.J. Wagner and K. Nahm, 6528–6530.

O

O

OH

Ohv

mechanism?

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Dane HolteBaran Group Meeting JACS: 1987 A Year in Review

Palladium-Catalyzed Reactions in the Synthesis of 3- and 4-substituted Indoles. 2. Total Synthesis of N-Acetal Methyl Ester of (±)-Clavicipitic Acids. P.J. Harrington, L.S. Hegedus, and K.F. McDaniel, 4335–4336.

NH

AcN

CO2Me

(±)-Clavicipitic Acid N-Acetal Methyl Ester

BrMe

NO2

1. Br2, hv, CCl42. PPh3

3. CH2O(g), Et3N (80% overall)

Br

NO2

1. Fe, AcOH2. TsCl, py.

Br

NHTs

5% PdCl2(MeCN)2benzoquinone

(80% over 3 steps)

Br

NTs

1. Hg(OAc)2, HClO4 (cat.)

2. I2 (97%)

Br

NTs

ICO2Me

NHAc

5% Pd(OAc)2, NEt3(60%)

Br

NTs

CO2Me

NHAc

OH

MeMe

8% Pd(OAc)2, NEt3P(o-tol)3 (83%)

NTs

CO2Me

NHAcOHMe

Me

15% PdCl2(MeCN)2

(95%)NTs

AcN

CO2Me

NaBH4, hv

Na2CO3, -20 ºC(74%)

Total Synthesis of (±)-Mitomycins via Isomitomycin A. T. Fukuyama and L. Yang, 7881–7882.

OMeMe

MeOOBz

N3

O

Ph

OEtS OTMS

SnCl4, -78 ºC2. 3N HCl, r.t. (98% overall) OMe

Me

MeOOBz

N3

O

Ph

OO

SEt1.

PhMe, 110 ºC2 hr (93%)mechanism?

OMeMe

MeOOBz

N

O

Ph

OO

SEt

N NH

R

MeO

O

OMe

OCONH2

R = OMe Mitomycin A

N

HN

O

O OMeO

O NH2

Me

MeO Al(OiPr)3, MeOH,r.t. 2 d (91%)

mechanism?

OMeMe

MeOOBz

N

O

Ph

NO

OH

OAr

H2N O Ar

40 ºC, 1 hr (87%)

Page 7: Baran Group Meeting JACS: 1987 A Year in Review Dane Holte · Baran Group Meeting JACS: 1987 A Year in Review Dane Holte Overview: 1987, vol. 109 ... H2, Ra-Ni, Et3N 2.Ph CH2 O, AcOH,

Dane HolteBaran Group Meeting JACS: 1987 A Year in Review

Cl

ClCl

ClClCl

SCl

Cl Cl

Cl

[4+2]Cl

ClCl

ClClCl

Cl

Cl

Cl

Cl

OOS

O O

PhMe, 110 ºC-SO2

Cl

ClCl

ClClCl

Cl

Cl

Cl

ClHH

Cl

ClCl

ClClCl

ClCl

Cl

Cl

85% overallkg scale?!

Li, tBuOH

SCl

Cl Cl

ClOO1.

2. Li, tBuOHH

HPd/C (10 eq)

"an intimate mixture"(ie. neat), 250 ºC,

sealed tube

254 nm hv

[6+6]

[4+2]

O

O

O

OO

O

[4+2]

Cu2O, quinoline,H2O, bipy.

150 ºC

1. B2H6, THF2. NaOH, H2O2

3. CrO3, H2SO4O

O

H OMe

O

NaH

O

OHOOH AcOH; then

TsN3, NEt3

O

ON2

N2

hv, MeOH

Wolff rearr.MeO2C CO2Me

1. KOH, EtOH

2. Pb(OAc)4, CCl4, I2, hvI I

Na-K, tBuOH

See also, Platonic Hydrocarbons group meeting (Shenvi, 2006)

"Pagodane": The Efficient Synthesis of a Novel, Versatile Molecular Framework. W. Fessner, G. Sedelmeier, P.R. Spurr, G. Rihs, and H. Prinzbach, 4626–4642.

Dytropic hydrogen transfer

Pagodane(24% overall)

OO O

Page 8: Baran Group Meeting JACS: 1987 A Year in Review Dane Holte · Baran Group Meeting JACS: 1987 A Year in Review Dane Holte Overview: 1987, vol. 109 ... H2, Ra-Ni, Et3N 2.Ph CH2 O, AcOH,

Dane HolteBaran Group Meeting JACS: 1987 A Year in Review

MeMe

Me

MeMe

H

(±)-LaureneneCrimmins, 6199–6200

Intramolecular Photocycloaddition. Cyclobutane Fragmentation: Total Synthesis of (±)-Laurenene. M.T. Crimmins, and L.D. Gould, 6199–6200.

MeMe

Me

O

Me

MeO2C

O

MeMe

13 steps

(27%)

MeMe

Me

O

Me CO2MeU filter,

>350 nm hv

100 ºC(87%)

1. LiAlH4, Et2O2. Swern Ox.3. Ph3P=CHCO2Et (89% overall)

MeMe

Me

O

Me CO2Et

1. Na, NH3, -33 ºC

2. H2, Pd/C, EtOH (80% overall)

MeMe

Me

O

Me CO2Et

1. LiAlH4, Et2O2. Swern Ox.3. TsOH, PhH (75% overall)

MeMe

MeMe

H H

O

various alkylations

MeMe

MeMe

H Me

RR

NaBH4,CeCl3

Luche(23%)

MeMe

MeMe

H H

H OH

MeMe

Me Me

H

HO1. KH,Bu3SnCH2I

2. nBuLi (57%) mech?

1. TsCl, py.

2. LiEt3BH (72% overall)

An Asymmetric Synthesis of (–)-Steganone. Further Application of Chiral Biaryl Synthesis. A. I. Meyers, J.R. Flisak, and R.A. Aitken, 5445–5452.

O

OO

MeO

MeOOMe

O

O

(–)-Steganone

OO

MgBr

OO

OMeMeO

MeOOMe

N

OPh

OMe

OO

MeO

MeOOMe

N

O

OO

THF, reflux

(65%)(7:1 mix. of diast.)

After asymmetric biaryl coupling,there are 9 steps before closing the 8-membered ring, with <10%racimization.

Ph

MeO

Synthesis of in-[34,10][7]Metacyclophane: Projection of an Aliphatic Hydrogen toward the Center of an Aromatic Ring. R.A. Pascal, R.B. Grossman, and D. Van Engen, 6878–6880.

H

HH

Page 9: Baran Group Meeting JACS: 1987 A Year in Review Dane Holte · Baran Group Meeting JACS: 1987 A Year in Review Dane Holte Overview: 1987, vol. 109 ... H2, Ra-Ni, Et3N 2.Ph CH2 O, AcOH,

Dane HolteBaran Group Meeting JACS: 1987 A Year in Review

Comprehensive list of all total syntheses (*formal):

O

NO

Cl

H NH3

CO2H

AcivicinWhitney, 276–277

MeH

MeCN

MeH

NCMe

7,20-DiisocyanoadocianeCorey, 287–289

(±)-CatharanthineRaucher, 442–446

O

OO

OMe

NH

OMe

Me

OH

Me

OH

MeAcO

MeMeO

O

MeOH

*Rifamycin SDanishefsky, 862–867

Roush, 953–955

NH

N

CO2Me EtN

O

H H

Me

HO

CO2

S

NH3

(+)-ThienamycinGeorg, 1129–1135

OO

O Ph

Me

O

H

H

(+)-PhyllanthosideSmith, 1269–1272Smith, 1272–1274

O

O

OHO

AcOHO

AcOHO

Me

O

Me

O

H

OH

OMe

MeOH

Me

MeOH

OH

OHMe

O

Et

HOMe

(+)-(9S)-DihydroerythronolideStork, 1565–1567

OMeO2C

Me

MeH H

Me

Me

OH

Me

OH

Me

OH

Me

OH

MeMeZincophorin

Danishefsky, 1572–1574

NN

N

O H

H H H

O

O

MeO

Me Me

CNHO

(±)-Cyanocycline AFukuyama, 1587–1589

HOMe OH

Me

HOOH

AphidicolinHolton, 1597–1600

N

N

MeOMe

H OHCO2Me

OCOMeEt

H

(–)-VindolineRapoport, 1603–1604

OH H

MeO2C

Me Et

Me

H Et

HO

HN

*IndanomycinDanishefsky, 2082–2089

O

O

Me

MeHO

Me

O OH OH

OH

OH OH

OH

CO2H

OAmphoteronolide B, Amphotericin BNicolaou, 2205–2208Nicolaou, 2208–2210NIcolaou, 2821–2822

HN N

HO2C

MeO OH

R

O

R = NH2 PDEIR = Me PDEII

Magnus, 2711–2717Boger, 2717–2727

OH

O

OH NH2

OHMe

CO2MeEt

O

Et

Me

Me

4-Methyl Juvenile HoromoneOgura, 2853–2854

OO

OO

O

OHtBu

OHO

H

(±)-BilobalideCorey, 7534–7536

Page 10: Baran Group Meeting JACS: 1987 A Year in Review Dane Holte · Baran Group Meeting JACS: 1987 A Year in Review Dane Holte Overview: 1987, vol. 109 ... H2, Ra-Ni, Et3N 2.Ph CH2 O, AcOH,

Dane HolteBaran Group Meeting JACS: 1987 A Year in Review

Comprehensive list of all total syntheses (Cont'd):

NMeO

MeO

O(±)-3-Demethoxyerythratidinone

Danishefsky, 917–918

O NH

O

O

HO

HO OH*(+)-Showdomycin

MeMe

OH

HO Me

HO H

(–)-Punctatin A,(+)-Punctatin D

Paquette, 3017–3024

H

Me Me

OH Me

Me

AfricanolPaquette, 3025–3036

MeOH

HMe Me Me

DactylolPaquette, 3025–3036

O

O

Me H

H

OH

O(±)-Grosshemin

Rigby, 3147–3149

O

�O

OH

OH

O

OO

MeOHHO

OMeH H

H

(±)-GranaticinYoshii, 3402–3408

O

AcHN

MeHO

OMe

(—)-N-Acetal-O-methylacosamineTrost, 3792–3794

NH

AcN

CO2Me

(±)-Clavicipitic Acid derivativesHegedus, 4335–4338

MeOH

H

H

Me

HMe Me(±)-2-Desoxystemodinone

White, 4424–4426

O

OHOHMe

(±)-CafestolCorey, 4717–4718

HOHO

C5H11

HO2C

d-(+)-CarbacyclinFuchs, 4755–4756

NMe

H(±)-Porantherine

Stevens, 4940–4948

O

OHO

OHOH

HMe

NHO

NH2Me(+)-Actinobolin

Kozikowski, 5167–5175

O

OOEt

OEtO

OOH

HO(–)-Specionin

Curran, 5280–5282

O

OO

MeO

MeOOMe

O

O

(–)-SteganoneMeyers, 5446–5452

HN

HO2C

O NH

CO2H

CO2H

Acromelic Acid ATakano, 5523–5524

O

OMe

MeOH

MeOEt

MeHO

d,l-MethynolideVedejs, 5878–5880

NO

O

H

OH

StreptazolinOverman, 6097–6107Overman, 6017–6114Overman, 6115–6118

Me

NH

N

O

O

OMeMeO2C

H

HH

MeONH

N

OHMeO2C

H

HH

(±)- ReserpineMartin, 6124–6134

(±)-α-YohimbineMartin, 6124–6134

OMe

OMe

OMe

Page 11: Baran Group Meeting JACS: 1987 A Year in Review Dane Holte · Baran Group Meeting JACS: 1987 A Year in Review Dane Holte Overview: 1987, vol. 109 ... H2, Ra-Ni, Et3N 2.Ph CH2 O, AcOH,

Dane HolteBaran Group Meeting JACS: 1987 A Year in Review

Comprehensive list of all total syntheses (Cont'd):

O

O

H HO

OC5H11

(+)-GloesproneSeebach, 6176–6177

OH

Me

CO2H

HO

(±)-AtractyligeninCorey, 6187–6189

MeMe

Me

MeMe

H

(±)-LaureneneCrimmins, 6199–6200

O

OO

MeMeMe

OH

OMe

OH

O

O

Me Me

OMe

OH

Br

AplysiatoxinKishi, 6205–6207

Me

Et H

H H

H

O

NH

NHO

O HH

*IkarugamycinWhitesell, 6403–6408

NH

Me

Pr

(+)-PulmiliotoxinSchultz, 6493–6502

HN N

MeO OH O

O

N

NH

N

O

HN

MeOMe

OH

O

NH2

CC-1065Kelly, 6837–6838

NNH

OH

OH

HN

OHO Me

OOHN O O

HN

OHMe

O

Me

HO

NH OHO

BuEchinocandin D

Evans, 7151–7157

O

O(–)-5-Hexadecanolide

Taber, 7488–7494

OO

Me

MeMe

HMe

ONH

N

O

HO2C NHMeCalicimycin

Boeckman, 7553–7555

OHO Me

OHOHOMe

H

OOHOH

HO

OlivinRoush, 7575–7577

N NH

R

MeO

O

OMe

OCONH2

R = OMe Mitomycin AR = NH2 Mitomycin CFukuyama, 7881–7882

NH

N

H

HEt

(–)-AspidospermidineFuji, 7901–7903

NH

N

H

Et

(+)-QuebrachamineFuji, 7901–7903

N

N

O Et

H

(–)-EburnamonineFuji, 7901–7903

O

OMe

OHOAc

OHMe MeH

MeOH

Me

*ForskolinZiegler, 8115–8116

OH

OMeMe

HOO O

OO

Me

MeH

MeMeH

O

O

Me

O

O

H

OMe

Me

HOMe

OMe

Avermectin A1aDanishefsky 8117–8119Danishefsky 8119–8120