Read JACS1986new.cdx text version

Baran Group Meeting

Selected Publishing Statistics for JACS 1986: Total number of papers: 1843 Total synthesis papers: 51 Leo A. Paquette 14 (1 total synthesis) Barry M. Trost 6 (2 total synthesis) Herbert C. Brown 4 (0 total synthesis) Samuel Danishefsky 4 (1 total synthesis) Gilbert Stork 4 (0 total synthesis) Amos B. Smith 4 (4 total synthesis) David Evans 4 (2 total synthesis) Larry Overman 3 (0 total synthesis) K.C. Nicolaou 3 (0 total synthesis) E.J. Corey 2 (0 total synthesis) Paul Wender 1 (0 total synthesis)

JACS: 1986 Year in Review

Syntheses Partially or Fully Discussed

HO H O O HO O O

Will Gutekunst

OMe MeO O O MeO NMe H

(­)-grandiosol

compactin

(±)-O-methylpallidinine

HO

O

OH

O O

HO OH

Manzamine A isolated Ryuichi Sakai, Tatsuo Higa, Charles W Jefford, Gerald Bernardinelli; 6404-6405.

MeO

mycophenolic acid Silphiperfol-6-ene

O

HO

(-)-punctatin A

Concerted!

H O O O O

OMe OH

O O

K.N. Houk, Yi-Tsong Lin, Frank K. Brown; 554-556.

H

pentalene

O

allamandin

OH CN N NMe O N

Protomycinolide IV

O HO2C N O O OH NH O

HO MeO Me O

O

OH H HO2C

jatropholone A

O

cyanocycline

Octosyl Acid

HO

Brevetoxin A Elucidated Yuzuru Shimizu, Hong Nong Chou, Hideo Bando, Gregory Van Duyne, Jon Clardy; 514-515

H H

O HO H O H OH CO2H

H

(±)-

(9,12)

-capnellene

pentalenic acid

(­)-coriolin

Baran Group Meeting

Total Synthesis of Mycophenolic Acid Rick L. Danhesier, Stephen K. Gee, Joseph J. Perez; 806-810. 1) NaBH4, EtOH 2) TBSCl, DMAP, TEA

OAc 3) K2CO3, MeOH OTBS

JACS: 1986 Year in Review

Will Gutekunst

CHO

OH

n-BuLi, MsCl Li2CuCl4

MeO MgBr

OTBS

Polyene Cyclization Strategy in the Stereospecific Synthesis of B/C-trans-Morphinan. A Total Synthesis of (±)-O-Methylpallidinine. Shinzo Kano, Tsutomu Yokomatsu, Hajime Nemoto, Shiroshi Shibuya; 6746-6748.

O OMe MeO MeO PhS O P(OEt)2 MeO MeO

70-75%

O O

85-95% LiCH2OMOM -78ºC, THF

OEt then, HCl workup O OMOM

1) n-BuLi, THF Sealed Tube Benzene 120o C, 14 hrs 73 % mechanism?

OH O H N O MeO O

name reaction MeO 1) KH n-Bu3SnCH2I MeO

OH 2) n-BuLi

HO

2) DBU 65%

OMe

+

OEt HO OH

78%

OMe MeO OMe MeO O O O N H O O O MeO NMe H

81%

TBSO O O MeO

O

1) NaBH4 2) HCO2H H 77%

O N O O

1) Br2, t-BuNH2 2) 2 eq. MeLi, 2 eq t-BuLi excess CO2 3) cat. HCl, MeOH reflux 60%

MeO

OMOM

PPh3 DEAD 99%

(±)-O-methylpallidinine

CrO3, H2SO4 -30ºC 61%

HO

O

OH

O O

Enantiospecific Total Synthesis and Absolute Configurational Assignment of (-)-Punctatin A Leo A. Paquette, Takashi Sugimura. 3841-3842. 1) LiAlH(O-t-Bu3) 2) SEM-Cl, Hunigs Base

O

MeO

O

1) LiAlH4 2) KH ICH2SnBu3

SEMO

O SnBu3

mycophenolic acid 17-19% overall The Total Synthesis of Octosyl Acid A: A New Departure in Organostannylene Chemistry Samuel Danishefsky, Randall Hungate; 2486-2487.

O TMSO O O OMe H O H O O HO O MeO2C NH N O MeO2C O NH N O HO2C OH OMe O

3)CH3SOCH2-Na+,

O I

DMSO

SEMO

48%

MOMO NH

15 steps

MeO2C

MeO2C MsO BnO H N

1) n-BuLi 2) MOM-Cl Hunigs Base SEMO 34%

MOMO OH

1) BH3-THF, diglyme; H2O2, NaOH, H2O 2) PCC, DCM 3) NaOMe, MeOH

MOMO O

85%

OMe O O

O

O

O

8.6%

SEMO

O NH N O O OH O

1) hv, 253.7 nm 2) TBAF 3) PCC, DCM

1) Me3SiCH2COOMe cat. TBAF, THF mechanism? 2) Pd(OAc)2, MeCN 32% for 5 steps

HO OH

MOMO OTMS

Bu2SnO MeOH

OBn OMsO

CsF DMF 77%

OBn H O MeO2C O

1) Pd(OH)2 2) LiOH, H2O

OH H

O

O

MeO2C

O Sn Bu Bu

O

1) NaBH4, CeCl3 2) DEAD, PPh3, PhCOOH 3) HClO4, THF/H2O 4) KOH, EtOH 62%

OH

HO2C

Octosyl Acid

HO

(-)-punctatin A

Baran Group Meeting

A Total Synthesis of Plumericin, Allamcim, and Allamandin Barry M. Trost, James M. Balkovec, and Michael K.-T. Mao. 4974-4983.

Ph Ph

BF4

JACS: 1986 Year in Review

Will Gutekunst

O NMe2 OEE BOMO Br

Stereocontolled Asymmetric Total Synthesis of Protomycinolide IV Keisuke Suzuki et. al. 5221-5229.

mCPBA, -78oC warm to 0oC 1) NaH, BOMCl 2) EtMgBr, TMSCl

OH

1)

S

TMS

PhSeBr DCM, py -45ºC 88%

O

KOH, DMSO 2) LDA, pentane 82% PhSSO2Ph LDA, THF

PhSe O

then add

O

3) DiBAL, Br2

OH

65-70% 1) mCPBA, DCM then, CaCO3 reflux 2) Ac2O, DMAP, py

SPh

O OBOM

1) MsCl, TEA 2) DiBAL, then AlEt3 DCM, -78oC to -20oC mechanism?

BOMO

n-BuLi/ Trapp solvent 4:1:1 THF:Et2O:hex -100o C, then H2SO4 92%

TMS OH

EtMgBr, 0o C

O O O PhS

OH

TMS

O O

-78o C 95%

then, CH3CHO

SPh

100%

O HO

steps

O O

75%

Protomycinolide IV

OH O O AcO

OsO4, NMO, H2O; NaIO4, H2O then NaOAc 3:1 E:Z 80%

O O

O O

O

FVT, 500o C .005 mmHg 81-90%

O

O O

O

O

Convergent, Enantiospecific Total Synthesis of the Hypocholesterolemic Agent (+)-Compactin Paul A. Greico, Randall Lis, Robert E. Zelle, John Finn. 5908-5919.

OMe

allamcin

O OMe OMe OH O O O MeO OMe O O O

1) LiAlH4, Et2O 2) NaH, MeI 3) Na, NH3(l) 71%

1) TsCl, py 2) NaI, MEK reflux 3) NaH, DMSO, 80oC

O PhO2S

1) CCl3COCl 2,6 di-t-Bu-py 2) Mg(OCH3)2 77%

O

0.01N HClO4 95oC - 100oC 55%

O

O O

O

OTr

OH

83%

MeO O OMe MeO OMe O

O

plumericin

allamandin

1)

TMS

1) Na(Hg), MeOH 2) LiAlH4 3) CrO3, py, celite

P(Ph)3

BuLi (9:1 E:Z) 2) TBAF 3) PhSH, AIBN HMPA, 150oC (3:2 E:Z) 42%

Total Synthesis of (+)-Jatropholones A and B, Exploitation of the High-Pressure Technique Amos B. Smith et. al. 2040-3048.

OMe

heat, 110-220 oC

PhO2S

CO2Me OMe

83%

O MeO OMe H O CO2Me MeO2C O PhS O

NR

MeO

O

Lewis acids

+

O

NR

OMe HO

O

5 kbar (71000 psi) neat 72 hrs 80%, single diastereomer

O

1) mCPBA, P(OMe)3, MeOH 2) DEAD, BzOH, PPh3 3) NaOMe, MeOH 4) Ac2O, DMAP, TEA 63%

O O

jatropholone A

SPh

Toluene 125oC 7:3 regioisomers 86%

Baran Group Meeting

MeO H O OMe MeO H O OMe

JACS: 1986 Year in Review

MeO H O OMe H O AcO TBSO HO O H O O O OH MeO Me OTBS O N NMe TBSO N O OMe Me N

Will Gutekunst

OAc O N NMe TBSO N O

1) MeLi, CuI, Et2O

MeO2C O H OAc

HO Me O

KH, Toluene 120oC 40% (50 brsm)

OH

OH OH N

OTBS MeO

OTBS

2) LiAlH4, Et2O 84%

N

Neat TFA

OTBS

1) LiBEt3H, THF 2) KHMDS, THF 68%

74-77% 2 steps

Me

Me

1) (S)-2-methylbutyric anhydride DMAP, TEA 2) 10% HCl, THF, then Ag(CO3)2/celite 3) BBr3, DCM 23%

OH O CN N NMe O N O

1) Li, NH3-THF 2) NaCN, pH 8.0 Tris 3) HF-py, MeCN, 50oC then, aq Na2CO3 to pH 10, O2 34%

MeO Me

compactin Stereoselective Synthesis of (±)-Cyanocycline David A. Evans, Carl R Illig, John C. Saddler

ClO2S N O Me N O NH2

cyanocycline

Et2O, -24 to -16oC; Na2SO3, K2HPO4

Me N

NH O

7 steps

O

Cbz N CN

1) H2O2, aq. Na2CO3 2) H2, Pd/C, CH2O 80%

H O Me N

Efficient Asymmetric (2+2) Photocycloaddition Leading to Chiral Cyclobutanes. Application to the Total Synthesis of (­)-Grandiosol A.I. Meyers, Steven A. Fleming; 306-307.

O HO O H2N OH O N H O

1) s-BuLi, MeI 2) s-BuLi, Ph2Se2; H2O2, py 62%

O N H O

H O

t-BuOK 82%

H O

1) MsCl, TEA 2) (PhSe)2, NaBH4

OH

N H

3) TFA, t-BuOOH 81%

OMe H O MeO Me N

N H

p-TsOH, toluene azeotrope water 81%

O N H O

1)

MeO

O O H H O MeO O

Me N HO OMe N Cl Me

DCM sat. with ethylene acetophenone -78ºC 93% (12:1)

6 steps

HO

N OMe O HO OMe Me

(­)-grandiosol

2) SOCl2 96%

Me N

SnCl4, DCM 9:1 d.r 56%

H Me N

Synthesis of Using Titanium Reagents John R. Stille, Robert H. Grubbs; 855-856. 1)Tebbe Reagent, DMAP, then 90ºC TsO CO2t-Bu 1) CpMgCl, THF mechansim? 2)Benzene, 75ºC 81% t-BuO2C

H H O

(±)-(9,12)-Capnellene

Cp2Ti

Cl

AlMe2

H O MeO O

N OMe HO OMe Me

1) LiBEt3H, THF 2) DDQ, MeCN/H2O 3) Ac2O, DMAP, py 4) Zn dust, TBSCl Hunig's base, DMAP 79%

O AcO

N OTBS TBSO OMe Me

1) OsO4, NMO 2) Et4NIO4

TBSO NH2

2) HOCH2CH2OH, TsOH benzene, reflux 81%

Tebbe Reagent

O

9 steps

H H

16-24 hrs

H

H

(±)-(9,12)-capnellene

Baran Group Meeting

JACS: 1986 Triquinane Year in Review

Will Gutekunst

General Transannulation Approach to Angular Triquinanes. Total Syntheses of (±)-Pentalenene and (±)-epi-Pentalenene. Goverdhan Mehta, Kasibhatla Srinivas Rao; 8015-8021. HCOOH, BF3

O O H

Intramolecular Photocycloadditions-Cyclobutane Fragmentation: Total Synthesis of (±) Pentalenene, (±)-Pentalenic Acid, and (±)-Deoxypentalenic Acid Michael T. Crimmins and Joe A. DeLoach;

O CO2i-Pr CO2Et

6 steps

hv uranium filter hexane 73%

HO

O

CO2i-Pr CO2Et

Li, NH3, THF, -78ºC 90%

90oC, 2 h 55%

H

H

4 steps

H

O

CO2i-Pr CO2Et

10 steps

CO2H

pentalene Asymmetric Total Synthesis of (+)-Penalenene via Chiral Sulfinylallyl Anions. Hydrolytic Ring Closure of Enol Thioether Ketones Duy H. Hua; 3835-3837.

O

pentalenic acid Total Synthesis of (-)-Coriolin Martin Demuth, Peter Ritterskamp, Eva Weigt, Kurt Schaffner; 4149-4145

O

2 eq O

S H

O S

O O H

1) Zn, AcOH

O

2 eq NaH, 2 eq MeI 45 min, then NaH, 18-crown-6 MeI, 195 h

O

O

H O

>20% acetone soln hv (300 nm), 6h 55-58%

O HO H O H OH H

(-) 2 eq

O

2 eq LDA, -78o C 91%

HO Ar H S H O

H

2) 88% HCO2H, CF3CO2H 60ºC, 24 h 57%

O H

(­) O

O

82% ee

H

4 steps

H

LDA 45% (±) (-) kinetic resolution via chiral sulfoxide

(­)-coriolin A General Approach to Linearly Fused Triquinane Natural Products. Total Syntheses of (±)Hirsutene, (±)-Coriolin, and (±)-Capnellene Goverdhan Mehta, A. Narayana Murthy, D. Sivakumar Reddy, A. Veera Reddy; 3443-3452.

O

pentalene

Tandem Radical Cyclization Approach to Angular Triquinanes. A short synthesis of (±) Silphiperfol-6-ene and (±)-9-Episilphiperfol-6-ene Dennis P. Curran, Shen-Chun Kuo; 1106-1107.

OEt O O O

benzene reflux 2h, 90%

O O

hv EtOAc 30 min 85%

O O

500ºC, 0.1 torr sublimation through quartz column filled with quartz chips quantitative

H H

3 steps

O

Bu3SnH 66% 1:3 C9 epimers

Br

9

NH2NH2

H H H H

45%

benzylbenzoate silphiperfol-6-ene

O H O

6 steps

H H O

317ºC, 12 min 37%

O

hirsutene

Baran Group Meeting

JACS: 1986 Year in Review

Generation of 1g O2 from Triethylsilane and Ozone E. J. Corey, Mukund M. Mehrotra, Ahsan U. Khan; 2472-2473. -78ºC

Et3SiH

Will Gutekunst

Use of Chiral Single Chrystals To Convert Achiral Reactants to Chiral Products in High Optical Yield: Application to Di--Methane and Norrish Type II Photorearrangements Stephen V. Evans, Miguel Garcia-Garibay, Nalamasu Omkaram, John R. Sheffer, James Trotter, Fred Wireko; 5648-5650.

CO2i-Pr i-PrO2C CO2i-Pr CH2O2i-Pr

ca -60ºC

Et3SiOOOH

+

O3

45 s

t1/2 ca 150 s

Et3SiOH

1O 2

80%, single enantiomer

O Ar HO

Chemistry of Dioxiranes 4. Oxygen Atom Insertion into Carbon Hydrogen Bonds by Dimethyldioxirane Robert W. Murray, Ramasubbu Jeyaraman, Lily Mohan; 2470-2472. DMDO 18 h, quant

Ar

OH

DMDO 18 h, 45%

OH

70%, 80% ee Titanacyclobutanes Derived from Strained Cyclic Olefins: The Living Polymerization of Norbornene Laura R. Gilliom, Robert H. Grubbs; 733-742.

Cp2Ti AlMe2 Cp2Ti

99% Chirally Selective Syntheses via Pinanediol Boronic Esters: Insect Pheromones, Diols, and an Amino Alcohol. Donald S. Matteson, Kizhakethil Mathew Sadhu, Mark L. Peterson; 810-819.

Cl

O

LiCHCl2

B

O Cl Cl O

ZnCl2 20ºC 86%, 200:1 dr LiCHCl2, -100ºC then, ZnCl2, 25ºC

N3 Cl

O B O

xs 65ºC

n

B O

Cl

-100ºC

N3 O B O O

DMAP

NaN3, Bu4NCl

O B O

Synthesis and Chemistry of Tetracyclo[8.2.2.22,5.26,9]-1,5,9-octadiene John E. McMurry, Gerogy J. Haley, James R. Matz, Jon C. Clardy, Gregory Van Duyne, Rolf Gleiter, Wolfgang Schafer, David H. White; 2932-2938.

O O O O

H2O/DCM quant.

H2NNHPO(OEt)2 91%

O O

O

O

HN P(OEt)2 N OR OR N N S S N N

BuMgCl, -78ºC 4 eq ZnCl2

N3

B O

1) H2O2 pH 7.6 2) LiAlH4 59% for 3 steps

OH

NH2

RO RO

N N N

N

OR

1) H2S, CH2CN

OR 2) Pb(OAc) , CaCO 4 3 RO RO

Chiral Synthesis bia Organoboranes. 8. Synthetic Utility of Boronic Esters of Essentially 100% Purity. Synthesis of Primary Amines of Very High Enantiomeric Puritys Herbert C. Brown, Kee-Won Kim, Thomas E. Cole, Bakthan Singaram; 6761-6764.

1) 37% HCl, DCM 2) toluene reflux then, (EtO)3P name reaction

O O

TiCl3, Zn/Cu 23% after recrystallizion of the sublimate

H B

5 steps

O B

1) H2NOSO3H 2)H2O, NaOH 99% ee

NH2

Baran Group Meeting

JACS: 1986 Year in Review

Will Gutekunst

Epoxy Silyl Ether Rearrangements: A New, Stereoselective Approach to the Synthesis of -Hydroxy Carbonyl Compounds Keiji Maruoka, Masaichi Hasegawa, Hisashi Yamamoto; 3827-3829. The Yamamoto Rearrangement

R1 R2 O R3 OTMS R4 R5 Ti R1 R2

Tandem Reactions of Alkynyliodonium Salts. Extremely Efficient Cyclopentene Annulations Masahito Ochiai, Munetaka Kunishima, Yoshimitsu Nagao, Kaoru Fuji, Motoo Shiro, Eiichi Fujita

O

TiCl4, DCM -78ºC, 10-30 min 50-95% yield

O R3 OTMS R4 R5

OH R1 R2

O R5

O O O IC6H5 BF4

t-BuOK t-BuOH mechanism?

O O O

O

93%

R3 R4

(most examples 45-75%)

O

OH OTMS Me Ph HO OTMS Ph

O

81%

O

O

79%

Seminal and/or Important Publications Epoxidation of Olefins with Cationic (salen)MnIII Complexes. The Modulation of Catalytic Activity by Substituents K. Srinivasan, P. Michaud, J.K. Kochi; 2309-2320. Palladium-Catalyzed Coupling of Vinyl Triflates with Organostannanes. Synthetic and Mechanistic Studies William J. Scott, J. K. Stille; 3033-3040.

Ruthenium Catalyzed Amidation of Nitriles with Amines. A Novel, Facile Route to Amides and Polyamides Shun-Ichi Murahashi, Takeshi Naota and Eiichiro Saito. 7846-7847.

R2 R3

3 mol % RuH2(PPH3)4 + 2 eq H2O DME, 160ºC, 24 h

R1

O N R2 O R3

R1 CN

+

HN

+

NH3

Catalytic Asymmetric Aldol Reaction: Reaction of Aldehydes with Isocyanoacetate Catalyzed by a Chiral Ferrocenylphosphine-Gold(I) Complex Yoshihiko Ito, Masaya Sawamura, Tamio Hayashi; 6405-6406.

C4H9 NH2 H N

+ MeCN

Me O

N H

C4H9

93%

Simple and Selective Method for RCHO -> (E)-RCH=CHX Conversion by Means of a CHX3-CrCl2 System Kazuhiko Takai, Kenji Nitta, Kiitiro Ultimoto; 7408-7410.

+ MeCN

Me

N

97%

Nonlinear Effects in Asymmetric Synthesis. Examples in Asymmetric Oxidations and Aldolization Reactions C. Puchot, O. Samuel, E. Dunach, S. Zhao, H. B. Kagan; 2353-2357. Catalytic Asymmetric Induction. Highly Enantioselective Addition of Dialkylzincs to Aldehydes M. Kitamura, S. Suga, K. Kawai, R. Noyori; 6071-6072.

O H2N CN N H

n

98%, Mn = 1600 mp = 175

Oxazoline Route to Azomethine Ylides Edwin Vedejs, Janet Wisniewski Grissom. 6433-6434.

R N

R1

X

R2 R3

PhSiH3, CsF

R1

R N O R2 R3

R R1 N O R2 R3

[3+2]

O

[2+2]

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