JOC Year In Review: 1993

Rohan Merchant
JOC Year In Review: 1993
Baran Group Meeting
04/18/2015
Statistics:
Volume 58
1540 papers
7957 pages
Publication record:
Wipf, P. (9)
Paquette, L. A. (9)
Padwa, A (8)
Olah, G. A. (8)
Marshall J. A. (8)
Top 5 Most Cited Papers:
Ig Nobels 1993
Chemistry: James Campbell and Gaines Campbell of Lookout Mountain, Tennessee,
dedicated deliverers of fragrance, for inventing scent strips, the odious method by which
perfume is applied to magazine pages.
Mathematics: Robert Faid of Greenville, South Carolina, farsighted and faithful seer of
statistics, for calculating the exact odds (710,609,175,188,282,000 to 1) that Mikhail
Gorbachev is the Antichrist.
Notable Events of 1993
Cost of a gallon of gas ~$1.16
Buckingham Palace opens doors to public
Pentium microprocessor introduced by Intel
World Wide Web was born at CERN
X-Files debuts
Michael Jordan retires for the first time
15 June 1993 - Formula One world champion James Hunt dies (45)
Shane Warne bowls "Ball of the Century" to Mike Gatting in the first Test at Old Trafford
EU Farmers protest the reduction in agricultural subsidies due to Maastricht Treaty
Top Movies:
Jurassic Park
Mrs. Doubtfire
Schindler's List
Cool Runnings
Top Songs:
I Will Always Love You by Whitney Houston
Whoomp! (There It Is) by Tag Team
Can't Help Falling In Love by UB40
Design, Synthesis, and Control of Conducting Polymer Architectures–Structurally
Homogenous Poly(3–Alkylthiophenes)
McCullough R. D., Lowe R. D., Jayaraman M., Anderson D. L. J. Org. Chem. 1993, 58,
904–912
757 citations
An Improved Procedure for the Preparation of the Dess–Martin Periodinane
Ireland R. E., Liu L. B., J. Org. Chem. 1993, 58, 2899
641 citations
New Nitric Oxide–Releasing Zwitterions derived from Polyamines
Hrabie J. A., Klose J. R., Wink D. A., Keefer L. K., J. Org. Chem. 1993, 58, 1472–1476
476 citations
A Convenient Reduction of Amino–Acids and their Derivatives
McKennon M. J., Meyers A. I., Drauz K., Schwarm M., J. Org. Chem. 1993, 58, 3568–3571
407 citations
Analysis of 2 C–13 NMR Correlations for Determining the Stereochemistry of 1,3–Diol
Acetonides
Rychnovsky S. D., Rogers B., Yang G., J. Org. Chem. 1993, 58, 3511–3515
358 citations
Heathcock; JOC, 1993, 58, 564–568
CN
Baran Group Meeting
04/18/2015
JOC Year In Review: 1993
Rohan Merchant
Fallis; JOC, 1993, 58, 2186–2195
Me
Me
Me
HN
1. Hg(NO 3) 2
2. NaBH 4
N
H
HCl, Δ
Me
39%
N
H
Me
O
59%
N
H
Me
MeLi,
THF
MeOH
86%
Me
Me
H
racemic
55%
Me
O
O
O
OH
O
Cl
Me
Me
C6H 6, Et 3N
N
NaOH, MeOH,
reflux, 48 h
HO
97%
Me
Me
HN
1. O 2, Pt, EtOAc
2. H 2, Pt, 0 °C
33%
HN
Me
HN
O
Me
Me
LiAlH 4,
THF
96%
HN
Me
HN
Me
HN
87–94%
Me
Alloaristoteline
H O
OH
First synthesis of
tricyclic core of Vinigrol
OTMS
KH, 18–Cr–6,
THF, reflux
O
80%
oxy–Cope
Me
Me
toluene,
µw, 2.5 h
H
H
O OMe
O
Me
O
97%
Me Me
OH
H
1. C6H 6, reflux
2. NaBH 4, CeCl3
Me
OMe
Me
Me
O
Me
Me
83%
Me
H
O
O
(63% 2 steps)
Me
60% (2 steps)
TMSO
H
O
Me
Me
Me
chromatography separation
of diastereoisomers
MeOH,
BF 3•Et 2O, rt
O
Me
Me
98%
H
R-(+)-isomer
O
Me
Devaux; JOC, 1993, 58, 2349–2350
O
Me
Me
HN
Me
Aristotelone
Me
Me
O
LiAlH 4
OH
1. MnO 2
2.
Me
MeO 2C
LDA, CdCl 2
HCl,
MeOH
OH
Me
Me
Me
Serratoline
HN
Me
NH
Me
O Me
Me
H
OMe
(+)-Longifolene
Ireland; JOC, 1993, 58, 2899
OH
H
CO 2H
I
OTMS
KBrO 3,
H 2SO 4
93%
use oxone
instead
O
O
I O
OH
Ac2O, 0.5% TsOH,
80 °C, 2 h
91%
O
O OAc
I OAc
OAc
In the absence of TsOH, difficult to obtain reproducible results for acetylation
DMP
Wang; JOC, 1993, 58, 1651–1652
Sheu; JOC, 1993, 58, 5784–5787
CHO ClMg
THF
HO
Me
Me
1. nBuLi
2. DMF
3. 0.1 N HCl
quant.
N
H
Baran Group Meeting
04/18/2015
JOC Year In Review: 1993
Rohan Merchant
N
H
H
O
R = H; 80%
R = Me; 81%
R = H; 93%
H 2SO 4
R = Me; 86%
Me
Me
H Me
26%
N
H
N
H
N
H
N
O
Me
N
Et
Cl
N
Cl
Me
N
conditions
N
N
N
Cl
N
Me
LiHMDS/THF, –10 °C, 2h
KOtBu/THF, rt, 5 min
R
R
Me
Me
R
Me
R
R
Me
B
Cl
N
O
N
N
Et
N
Me
A
17%
54%
O
Me
Me
Davis; JOC, 1993, 58, 1751–1753
N
O
N
N
Et
A
N
OMe
Me
N
MeO
MeO
OH
S
O2
O
1. NaHMDs
2. 1, THF
50%, 94% ee
OMe
MeO
Me
B
76%
22%
O
O
Me
N
Conditions
NHMe
N
Me
O
NH
R = H; 50%
R = Me; 13%
name rxn
Proudfoot; JOC, 1993, 58, 6996–7000
N
O
Et
N
N
H
N
H
Yuehchukene
Me
N
Me
H
H
N
H
benzene, reflux
R
Me
Me
H Me
R
2. 2–aminoethanol
Me
H
TMS
HO
TMS
Me
Me
Me
9–BBN
Me
50%
TFA, (CH 2OH) 2,
150 –155 °C
R
1.
asymmetric hydroxylation
Cl
Cl
1
N
O
O
O
HO
OMe
OMe
MeO
O
OH
OMe
OMe
Kuehne; JOC, 1993, 58, 7482–7489,
Kuehne; JOC, 1993, 58, 7490–7497
Grabowksi; JOC, 1993, 58, 5886–5888
(PhO) 2PON 3, DBU,
toluene, 0 °C to rt
OH
R
R = Ar, Alkyl
Het. Ar
H
N
OPO(OPh) 2
80–90%, ~95% ee
N3
N3
N
R
OH
NBn 2
R
N
H
O
N
H
O
Bn
N
99.6% ee
(PhO) 2PON 3, DBU
91% yield
(97.5% ee)
EtO 2CN NCO 2Et
(PhO) 2PON 3, PPh 3
(Mitsunobu cond.)
81% yield
2 x FCC,
(82% ee) 1 distillation
1%
silica–gel
filtration
N
H
6–8%
N
H
Me
H
N H H
CO 2Me
N H
CO 2Me
Me
N
CO 2Me
expected product
not formed
"unexpected Heck"
N
H
N
reflux
CO 2Me
N
H
H
L
N H Pd
L
O
MeO
Me
N
H
H
Me
H PdLn
N H
MeO
O
N
H
PdLn Me
N H H
CO 2Me
OH
Pd/C, H 2,
MeOH
67% (2 steps)
CO 2Me
thermodynamic product
N
N
H
N
N
H
OMe
CO 2Me
Ph
O
Me
84%
N
H
CO 2Me
OMe
Me 3SI,
tBuLi, THF, Name Rxn
–20 to 45 °C
Rawal; JOC, 1993, 58, 5583–5584
N
H
Bn
N
51 % (2 steps)
Bn
N
5% Pd(OAc) 2,
K 2CO3, DMF,
nBu 4NCl, 80 °C
CHO
OMe
BF 3•Et 2O,
toluene,
110 °C, 18 h
CO 2Me
10% HClO 4/THF
rt, 5 h
CHO
Practical Alternative to Mitsunobu Conditions for
activated alcohols to azides
NH
NHBn
MeO
N3
O
I
Baran Group Meeting
04/18/2015
JOC Year In Review: 1993
Rohan Merchant
O
Strychnine
O
N
H
OH
CO 2Me
Bosch; JOC, 1993, 58, 7756–7767
Weinreb; JOC, 1993, 58, 4945-4951
O
THPO
Bn
Cl
N
NBn
OH
BnN
OTHP
44%
OH
H Bn
N
TsN
H
O
BnN
H
H Bn
N
H
H
MeO 2C
TMS
FeCl 3, CH 2Cl 2,
–78 C to rt
H
61%
TsN
NBn
NBn
H
H
Sarain A core
H
H
H
OH
71%
Yamamoto; JOC, 1985, 50, 4412–4414
Org. React. 2001, 58, 9
Me
Me
Me
OR
A: Et 2Zn, CH 2I 2, Et 2O, rt
B: iBu 3 Al, CH 2I 2, CH 2Cl 2, rt
C: Sm/Hg, CH 2IX, THF, –78 C to rt
Me
Me
OR
Me
Me
Me
Me
R A
H 74
Bn 97
C
1
67
98
75
2
76
0
Bn 1
0
0
OR
H 3
Bn <1
Cl
H
4
0
0
0
Et 3N
N
MeO 2C
H Me
O
H
1. Lawesson's reagent
2. NiCl 2, NaBH 4, MeOH
H
(30 % 2 steps)
Me
H Me
H N
H
N
MeO 2C
H Me
(±)-2,7-Dihydropleiocarpamine
NiCl 2
Me
Me
H
H N
Cl
61%
N
MeO 2C
NaBH 4, ROH
RSR'
Ni 2B
Ni 2B + H 2
RH + R'H
Me
Me
Me
NaSPh
Cl
D
Me
LiBEt 3D
H
Me
Me
O
Back; JOC, 1993, 58, 2407–2413
B
H
OR
Me
MeO 2C
complementary
to the usual
Simmons–Smith
cyclopropanation
55%
H N
N
Al(Me)3 (3 eq.)
CH 2I 2 (2 eq.),
CH 2Cl 2, rt
O
H N
H Me
Et 3SiH–TFA
(50%)
TsN
Price; JOC, 1993, 58, 3589–3590
Me
OH
N
Cl
h ν,
MeOH–H 2O,
15 min
H N
MeO 2C
H
H
CO 2Me
O
TMS
MeO 2C
CO 2Me
H
OTHP
NBn
N
33%
O BnN
BnN
H
i. LDA,
THF, –70 °C
ii. HCl, rt
N
320 °C,
DCB
THPO
OH
Baran Group Meeting
04/18/2015
JOC Year In Review: 1993
Rohan Merchant
PhS
NiCl 2, NaBD 4,
MeOD
H
H
mild desulfurization
conditions
Stereoretentive!
Overman; JOC, 1993, 58, 2468–2477
OH
O
OBz
OH H
Chen; JOC, 1993, 58, 4520–4521
O
BF 3•Et 2O,
23 °C
O
H
O
OBz
71%
H
Prins cyclisation –
Pinacol rearragement
O
Br
H
NHBzO
OBz
O
Me
Ph
O
OCO 2Bn
NaOMe,
MeOH
O
O H
H
H
(±)-kumausallene
HO
Li MeMg(HMDs) 2
R
toluene
NHBzO
Ph
HO
Me
10
O
OH
O
OH
Cl
R
Et 2N
Moriarty; JOC, 1993, 58, 2478–2482
PhI(OAc) 2,
KOH, MeOH
R
NH 2
70–90%
R = Alkyl, Ar, Het Ar
O
O
R
Ph
MeO
I
N
OMe
H
O
R
R
F
–PhI
Ph
–MeO–
I
N
OMe
HO
Et 2NCF 2CHFCl,
CH 2Cl 2
47%
O C N R
MeOH
PhI(OMe) 2
R
H
N
OMe
O
O OTroc
Me
NHBzO Me F
Me
Me
AcO
OBz
O
OH
"relatively safe fluorinating
agent that is easy to use"
–EROS
HO
O
13%
N
N
RM
SO2Ph
H
N
R
N
N
RM
N
SO2Ph
A
SO2Ph
B
DDQ
KOH,
PhI(OAc) 2 MeOH
O
(Yarovenko reagent)
OMe
O
Me
AcO
OBz
Padwa; JOC, 1993, 58, 2061–2067
SO2Ph
analogous to
Curtius rearrangement
H
N
O
Me
OH
O OTroc
Me
Me
Me
AcO
OBz
O OTroc
Me
O
Ph
Cl
Yarovenko reagent
The new reagent provides clean product with complete
suppression of impurities
esters to methyl ketones
O
AcO
OBz
NHBzO
F F
Weinreb's procedure provided the methyl ketone in 71 %
yield, along with several impurities (0.5-1%) which were not
easily removed without a yield penalty
N
O
OCO 2Bn
Me
Me
75%
R=
O
O
7
Ph
Ph
dr = 10–12:1
OMe
7
O
HO
O
Me
Me
AcO
OBz
AcO
Me
NHBzO
DAST,
CH 2Cl 2
80–90%
Chen; JOC, 1993, 58, 2927–2928
Reider; JOC, 1993, 58, 3731–3735
2 x LiHMDs + MeMgCl
OH
O OH
Me
OH
MeO 2C
Br
19
AcO
7–epi Taxol
Me
H
H
H
H
83%
O
Baran Group Meeting
04/18/2015
JOC Year In Review: 1993
Rohan Merchant
possible method to get
around alkylation selectivites
for pyrazoles?
R
N
N
SO2Ph
NaH
MeMgBr
nBuMgBr
sBuMgBr
PhMgBr
tBuMgBr
MeLi
nBuLi
sBuLi
tBuLi
A
B
100
0
0
100
0
100
0
100
0
100
12
88
50
50
17
83
67
33
33
67
Albizati; JOC, 1993, 58, 291–293
Altamura; JOC, 1993, 58, 272–274
i. DDH, aq. MeCN
OBn ii. CSA, CH 2Cl 2
HO
O
O
O
O
OBn
O
75%, 15:1 dr
Me Me
OH
O
Me Me
Oxidative rearrangement
OTBDMS
H
S
Me
N
O
O
Me
Me
NH
O
O
N
H
DDH/DBH
HO
via
O O
O
OBn
Me
Me
O
OMe
Me
Me
O
Trioxa-Tricyclic Subunit
of Saponaceolides
1. NaH
2. CuX 2, DMSO,
40 °C
E1
E1 /E2
Paquette; JOC, 1993, 58, 4245-4253
PPA,
AcOH,
100 °C
80%
O
O
OH
61% (2 steps)
Me
Me
O
FeCl 3,
DMF, –78 °C
O
X = Cl/Br
NIS, Ag(OTf), 150 °C; 45%
Bn 2N
Me
I
"very reactive
superelectrophile"
OsO 4 (cat.)
Jones reag.
acetone/rt
65%
Bn 2N
CO 2H
Presence of basic nitrogen does not interfer withe the reaction.
Mildly acidic conditions – protection of basic nitrogen as ammonium salt
H
Me
H
O
Me
O OH
S
I TfO
F 3C
O
O 2N
Weinreb; JOC, 1993, 58, 4745
Me
H
O
H
X
tolerates double and triple
bonds along with allylic and
benzylic moeities
E
NIS, TfOH, rt, 86%
O 2N
40%
H
H
No need for
chromatography
O
Olah; JOC, 1993, 58, 3194–3195
LDA (2 eq.),
THF, –78 °C
KHMDs,
88%
THF, Δ
Me
70–90%
= EWG
O
intramolecular
oxidative coupling
H
X = Cl, 90%
X = Br, 85%
X = I, 75%
X
O
O
Me
H
E
for highly electron deficient aromatics
71% (2 steps)
Me
O
Me
1. Ph 3P CH 2
THF–HMPA, –78 °C
2. H 2C CHMgBr
THF, 0 °C
HO
O
OTBDMS
H
S
Me
DMSO,
rt, 3 h
N
O
mild halogenation
O
conditions
CaX 2,
Dai; JOC, 1993, 58, 4596–4598
O
E2
1. CH 2(CO 2Et) 2,
Na, EtOH
2. KOH, HCl
OMs
applied to other allylic and benzylic systems
Me
"widely used as a
disinfectant used for
drinking water purification"
O
Baran Group Meeting
04/18/2015
JOC Year In Review: 1993
Rohan Merchant
H
Me
Me H
CO 2H
Cerorubenic Acid-111
Some useful modifications
Malacria; JOC, 1993, 58, 4298-4305
Simpkins; JOC, 1993, 58, 533–534
O
TMS
Baran Group Meeting
04/18/2015
JOC Year In Review: 1993
Rohan Merchant
TMS
O
I
BuLi, TMEDA
O
O
90%
Me
N
Me
OH
Ph
Ph
O
O
1. HCO 2H, CuSO 4
79% (2 steps) 2. (MeO) 2POCH 2CO 2Me,
tBuOK
TMS
TMS
i. 1, Additive,
THF
ii. PhCHO
Me
N
Me
N
Li
1
ee (%)
Additive
24
None
LiCl (0.5 eq.)
78
Ph
Trost; JOC, 1993, 58, 1579–1581
TMS
AcO
TMS
SiMe3
H
CO 2Me
O
i. KH, THF
ii. 2, toluene,
CuSO 4, 110 °C
Pd(OAc) 2, (iPrO) 3P
CO 2Me
PivO H
90%
[3+2]
TMS
TMS
KF, DMSO
S
S
H
74%
PivO H
N
O
SH
NBS, MeOH
S
S
N
OMe
S
O
enone formation while avoiding oxidation step
2
Badet; JOC, 1993, 58, 1641–1642
95%
TMS
TMS
5% CpCo(CO) 2,
136 °C, h ν
81%
CO 2Me
3,
THF/DMF
RH
R
N OH
HO 2C
O
N2
TMS
CO 2Me
TMS
O
O
O
RH = Ar/Alkyl amine, phenols,
thiophenols, peptides
N
NHTs
DCC
N O
O
mild diazoacylating agent
O
N2
3
bench stable
[2+2+2]
75%
retro 4 π e[4+2]
Yamamoto; JOC, 1993, 58, 3791-3793
decane,
175 °C
OH
Me
TMS
CO 2Me
H
H
TMS
TMS
CO 2Me
H
H
iPr 2EtN
OH
OAc
Me
yield
(%)
86
1° OAc:
diacetate
95.7:4.3
92
98.5:1.5
collidine
Bulky bases (iPr 2EtN or collidine) give better selectivity than Et3N, pyridine
FYI!
Extends to other acyl chlorides and silyl chlorides as well
Roskamp; JOC, 1993, 58, 4142–4143
TMS
15%
base
AcCl (1.2 eq.),
Base (2.0 eq.)
OH CH 2Cl 2, –78 °C
75%
O
Ph
O
SnCl2•2H 2O
CH 2Cl 2, rt
O
Ph
H
no promoter; 38% (16 h)
naphthalene; 53% (2 h)
C60; 63% (3 h)