Yuzuru Kanda Chemistry of -extended Molecules Baran lab Group … · 2016-10-29 · NaBH 4 Me Me Me...
Transcript of Yuzuru Kanda Chemistry of -extended Molecules Baran lab Group … · 2016-10-29 · NaBH 4 Me Me Me...
Chemistry of π-extended MoleculesYuzuru Kanda Baran lab Group Meeting5/7/16
polymer
Harold Krotopassed away30 Apr. 2016
http://www.extremetech.com/extreme/210872-extremetech-explains-what-is-moores-lawhttp://www.telegraph.co.uk/obituaries/2016/05/02/sir-harold-kroto--obituary/https://www.cheaptubes.com/product-category/multi-walled-carbon-nanotubes/Chem. Rev. 2006, 106 , 11, 4455. Nature 2003, 424, 915. Dalton Trans. 2010, 39, 4107. JACS, 2012, 134 , 9380. Science 2015, 347, 646.
1996Harold Walter KrotoRichard Errett SmalleyRobert Floyd Curl
2010Andre Konstantin GeimKonstantin Sergeevich Novoselov
– Ultimate goal of π-extended molecules is application for nano devices
oligothiophene
Moore's law– the number of transistors in a dense integrated circuit doubles approximately every two years.
???
NNH
N HN
N
NHN
N
N
HN
N
N
will not cover...
corrole
NNH
N N
corrin (GM; Tian, 2016) Phthalocyanine
N NB
F F
catenane(GM; Ishibara, 2010)
BODIPY
rotaxane
supramolecules
fullerene isomersmulti wall nanotubes
carbon nanohorn
S
S
S
S
S
SS
S
π molecules = Flat
1. efficient electronic interactions between individual segments2. efficient energy transfer3. uniform molecular structure (uniform property)4. robust and stable structure5. easy to process (solubility, toxicity, reactivity)6. mass production
How manyπ electrons?
Planar?
Planar?
4n+2
4n
aromatic
antiaromatic
nonaromatic
nonaromatic
Hückel system
reverse in Möbius system
✔
✔
✘
✘
β-position
Yuzuru Kanda
Porphyrin Rothemund Synthesis
NH H
O
H N
NH N
HN
1. cat. HCOOH2. Chloranil
~ 10% yieldafter 2-3 column
JACS. 1935, 57, 2010.JACS. 1936, 58, 625.
R
O
Hcat. H+
~ 60%R
NH HN H
O
R'
1. cat. H+
2. Ox
~ 60% N
NH N
HN
R
R'
R
R' OPRD. 2003, 7, 799.
N
N N
N
Ar
Ar
Zn
9.2 ppm9.4
10.3N
N NN
Ar
Ar
ZnN
N N
N
Ar
Ar
ZnAgPF6, CHCl330ºC, 5 h
w/ cat. I2, 5 min47% S.M. + 27% dimer + 4% trimer
purified by GPC
N
N N
N
Ar
Ar
Zn HH
128106 nmstable
soluble to CHCl3, THF
N
N N
N
Ar
Ar
Zn HH
10240.85 µm
C65536H83970N4096Zn1024 (M = 1,061,658)non detectable by MALDI-TOF
Chem. Eur. J. 2005, 11 , 3389.
NH HN
Me
Et
Me
Me
Et
Me Br
Cu(OAc)2
9% N
N N
N
Et
Me Me
Et
Et
Me
Et
Me
Cu
J. Chem. Soc. 1961, 2418.
NH HN
Mes
N N
Mes1. NXS; DDQ
2. Ni(OAc)2 NiX X
X = ClNa2S•9H2O
N
NS
N
NS
Mes
Mes
Ni
X = BrNaN3, CuI
NN
Mes
XX
N
NN
N
NN
Mes
Mes
Nimeso-position
X = BrNiCl2, PPh3
Zn
DMF, 45 ºC30 min, 90%[gram scale]
NN N
N
Mes
Mes
Ni
Norcorroleantiaromatic
ACIE. 2012, 51, 8542.Inorg. Chem. 2002, 51, 12879.Chem. Eur. J. 2012, 18 , 16129.aromatic nonaromatic
PPh3
TMS
TMS
TMS
H
O
H
MeLi TMSTMS 1. Li; H2SiCl22. CHBr3 Si
TMS
TMS
TMS
TMSBr Br
SiTMS
TMS
TMS
TMS
– air- and moisture- sensitive crystal– the first isolable dialkylsilylene
JACS. 2004, 126 , 9993.ACIE. 2014, 53, 1506.
KC8 Ni(II)-norcorrole
toluene, rt, 30 min97%
NN N
N
Mes
Mes
Ni
SiR
R
N
N N
N
Ar
Ar
Zn Ar'Ar'
12
DDQSc(OTf)3
N
N N
N
Ar
Ar
Zn Ar'Ar'
12
electronic wireextreme red-shift;
~3500 cm-1
Science 2001, 293, 79.J. Phys. Chem. A, 2003, 107 , 8792photonic wire
oxidative dimerization; ACIE. 1997, 36, 135.
selected examples of hetero-porphyrins
tBuSi
tBu
Cl Cl Li, Na
THF82%
SitBu
tBu in situ SitBu
tBuJACS. 1999, 121 , 9722.
✔ norcorrole (antiarom)✘ porphyrin (arom)
taking advantage of antiaromaticity
Chemistry of π-extended Molecules Baran lab Group Meeting5/7/16
18π1.47 ppm1.57
16π
Yuzuru Kanda
N
N
N
N
Mes
MesMes
Mes
NiNH2
DDQ, TFA N
N
N
N
Mes
MesMes
Mes
Ni NN
NN
NN
Mes
MesMes
Mes
Ni
N
N
N
N
Mes
MesMes
Mes
Ni NN
NN
NN
Mes
MesMes
Mes
Ni N
N
N
N
Mes
Mes Mes
Mes
NiNN
NN
NN
Mes
Mes Mes
MesNiN
N
twisted angle = 300º
N
N N
HN
Ph
Ph
Ph
PhNi(acac)2
57%COOEtH
N
N N
N
Ph
Ph
Ph
Ph
EtOOC
NiN
N N
N
Ph
Ph
Ph
Ph Ni
H
COOEt
N
N N
NPh
Ph
Ph Ni
H COOEt
homoporphyrin
N
NH N
HN
Et
Et HN Et
Et
Et
Et
Et
Et
COOEt
N
NH N
HN
Et
Et Et
Et
Et
Et
Et
Et
NCOOEt
Δ or M+
aza-homoporphyrinunstable
[2+2]hν
50%
Möbius (4n)mederately aromatic
Hückel (4n+2)non-aromatic
CN
CNNC
NCD.A. w/
Hückel product
pureMöbius product
Nature, 2003, 426, 819.
phasechange
NH
CHO
MeSO3H; DDQ
DCM, 0 ºC, 2 h
F
FF
F
F N
NH N
HN N
HNN
NHArAr
Ar
Ar
Ar Ar
Ar
Ar
P4/P6/P8/P10 = 9:19:38:15 (%)TL, 2003, 44, 2505.
1. POCl3, Et3N, DCM2. POCl3, Et3N, toluene
P6N
N
NNH
Ar
Ar
Ar
Ar
N
NP
O
Ar
ArP
O
Möbius anti-aromatic (30π)stable @rt
ACIE. 2010, 49, 4950.
AcOH
NH
Ar
ArN
HN
Ar
Ar HNAr
N
HN
OF
FF
F
Möbius aromatic (28π)stable w/o metal @rt
JACS. 2009, 131 , 7240.
highly twisted and fully conjugated system; JACS, 2015, 137 , 142
Chemistry of π-extended Molecules Baran lab Group Meeting5/7/16
breaking aromaticity; TL, 1974, 36, 3155. JACS, 1975, 97, 6175
Möbius aromaticity; TL, 1964, 29, 1923.
Möbius strip– A surface with only one side and only one boundary.
OsMeOOC PPh3
2BF4
Planar Möbius aromaticy;Nat.Commun. 2014, 5, 3265
12.0811.94 ppm
9.489.04
16π
Baran lab Group Meeting5/7/16Yuzuru Kanda
0D carbon material: Fullerene– the largest particle posessing wave-particle dualitytotal synthesis(?) of C60; Science 2002, 295, 1500.
O
Cl
6 stepsto prepare Cl
trimerization
TiCl4
FVP
1100 ºC0.1-1%
Name reactions in fullerene– Bingel reaction
C60DBU
tolueneEtO
O
OEt
O
Br– Prato reaction
R
O
H MeHN
O
OH toluene
C60
O
EtO
O
OEt
C60C60
NMe
R
H2O
H2O
Molecular surgery; Science 2011, 333, 613.
C60N N
Ar Ar
1-ClNaph260 ºC, 40 h
O2, hν
1-ClNaph, CS2rt, 23-27 h
29%
ArAr ArAr
[4+4]
ArArretro [2+2+2] OO
ArAr
NMMO
THFrt, 3 h89%
OO
ArAr
O
O
H2O OO
ArAr
O OHHO
H2O
120 ºC36 h
9,000 atmquant
OO
ArAr
O OHHO
P(OiPr)3
toluene120 ºC
15 h, 50%
ArAr[4+2] thenretro [4+4]
Al2O3
360 ºC, 1 h29%
H2O@C60X ray was taken as
(Ni-porphyrin)2H2O@C60
Chem. Eur. J. 2003, 9, 1600.
recent example; 2H2O@C70Nat. Chem. 2016, 8, 435.
kg-scale synthesis of corannulene; OPRD, 2012, 16 , 664.
MeCl Mg;
O
OMe
OMe
85%
Me H2SO4AcOH
71%
MeMe
MeO OMe
MeOH
MeMe
O O(COCl)2AlBr3
73% (2:1)
MeMe
O O
Girard reagent T
AcOH85%
MeMe
O N
3-pentanoneKOH
MeMeOH
MeMe
O
norbornadiene
Ac2O60% (2 steps)
MeMe
MeMe
NBSAIBN
hν
90-95%
Br Br BrBr
Br
Br
Br
Br HCOOHEt3N, Pd/C
88%
NaOH aq.
79%
R
R
R
R
Corannulene
R = BrR = H
NH O
Me3N
Chemistry of π-extended Molecules
no column8 steps (8.7%)
1.3 kg preparedTCI: $814 /100 mg
Me
O
Yuzuru Kanda
bent aromatics: [n.n']Paracyclophane
O
Br Br
O
Br Br
4-10
SS
O4-10
Na2SAl2O3
1. (MeO)2CHBF42. KOtBu
OO
4-10
SMe
SMe
1. (MeO)2CHBF42. KOtBu; DDQ O O
4-10
JOC. 2003, 68, 2089.
iPr MeSO
p-tolO
Li
TsSe
2
the smallest model for CNT
TsSe
GeranylClNaBH4
Me
Me
Me
Me
mCPBA;Et2NH
88%
Ox from less hinderd face
Me OH
(S)-Linalool
HN
O
NH
OH
TBAF, MS 3 Å;Ac2O, Et3N, DMAP
DMSO, 85ºC45%
single atropisomer
sanjoinine G1
F
NO2
Me
MeO
NBn2
OHMe
Me
OO2N
NHO
HN
OMe
MeBn2N
MeMe
OAc
NO2
F
Ph
NH2
OH
TBAF
THFMS 3 Å
40%
NO2
ONH
Ph
NO2
[2.2]Paracyclophane as a chiral auxiliary; JOC. 1991, 56, 5672.
JACS. 2002, 124 , 583.
n
n'
to close the ring...
RCMMcMurryRamberg-BäcklundWittig
NH
NH2
cyclophane closure in total synthesis
4 stepsN N
N
NMeOOC
N
N
H
COOMeinverse electron demand D.A.
N,N-diethylniline
100%
Rawal's intermediate8 steps (15.8%)3 steps N
HN
H
O
ACIE. 2002, 41, 3261.
Chemistry of π-extended Molecules Baran lab Group Meeting5/7/16
NCOCF3
F3COCNhν
hν
33%octahedrane
[5-5-3-5-5-5-5-3-5-5]fused ring system
JACS. 2006, 128 , 16508.
shorter N-C bond
through-bond interaction
HO
HOOTs
ClOTBS
TESOTESO
Cl O
O
NHAc
H
HO
HOOTs
ClOTBS
HOO
Cl O
O
NHAc
H
CsF, MS
DMF, 100 ºC
Cs
HO
HO
ClOTBS
HOO Cl O
O
NHAc
H
60% + 8% regioisomerno atropisomer isolated
fijiolide A
JACS, 2015, 137 , 11278interesting reactivity of cyclophane
NNO
CF3O
F3C
NCOCF3F3COCN
not yet made!!! (calc. predicted inpossible)
Chemistry of π-extended MoleculesYuzuru Kanda Baran lab Group Meeting5/7/16
1D carbon material: Carbon nanotube (SWNT)
Phanephos; JACS. 1997, 119 , 6207. (from Merk Process)
Phanephos
PPh2
PPh2
Br2, Fe
ratio?Br
Br Br
Br
triglyme, 230 ºC1/1 = S.M. + desired
+
1. tBuLi;MgBr2•Et2O;PPh2(O)Cl
2.
NaOH
PPh2
PPh2
O
OHOOC
OBzCOOH
OBz(R)
47% (2 steps)>99.5% ee
;
HSiCl3
p-xylene87%
R2R1
R3HNOMe
O
R2R1
R3HNOMe
O
[Rh(cod)Phanephos]OTf(1-2 mol%)
H2
MeOH, rtupto 99.6% ee
kinetic resolution of peroxides; JACS, 2007, 129 , 3836.Me OOH
Me
MeMe OOH
Me
Me
PAr2
PAr2
Ar = 3,5-Me2C6H3
L
86% ee
inseparable
HO MeMe
Me
1. Et3SiCl, Et3N2. TBAF
> 99%ee
L =
Me OOHMe
Me
sigma$90.10 /100 mg
chiral boronic acid containing cyclopropane; JACS, 2003, 125 , 7198.
OBH
OMeMe
MeMe
Me
MeOOC
Me
MeOOCB
OO
MeMe
MeMe
[Rh(cod)Cl]2 (3 mol%)Phanephos (6 mol%)
89%>99/1 cis/trans, 97% ee
R1
R2
R1
R2
enantioselective Cope rearrangement; Nat. Chem. 2012, 4, 405.(S)-L(AuCl)2 (5 mol%)
AgSbF6 (20 mol%)
98-23%93-58% ee
Me
OH
Me
NPth
eg)
Me LPtCl2AgBF4
Ph3COMe
Me
O
Me
O
MeEtR
61%87% ee
76%64% ee
O
MeR = F80%
81% ee
OH
LPtCl2, AgBF4 NCC6F5
TMDOMe, XeF2
R
FMe69%
10% eeF
OH
Me
enantioselective polyene cyclization; ACIE, 2008, 47, 6011. JACS, 2013, 135 , 628.
roll up
Hex
Yuzuru Kanda
I
I
MeO OMe
Bpin Bpin
MeO
MeO
OMe
OMe
MeO OMe
I I
nBuLi(iPrO)Bpin
Ar-IPd(PPh3)4
Cs2CO3
toluene/MeOHm
m = 2, 2%m = 3, 10%m = 5, 10%
LiNaph
includes at leastone homo coupling
separableby column
MeO MeO
e–
m
m = 4, 43%m = 7, 52%m = 13, 36%
1-2. Itami's strategy; ACIE. 2011, 50, 3244.
MOMO
MOMO
I
I
Ni(cod)2bpy
27%
MOMO
MOMO
MOMO
MOMO
NaHSO4, airm-xyleneDMSO65%
[12]CPP
3 steps13% yield
OMOM
OMOM
OMOM
OMOM
1-3. Yamago's strategy; ACIE. 2010, 49, 757.
SnMe3
SnMe3
PtL2L2Pt
L2Pt PtL2
PtCl2(cod)
57%
L = codL = dppf
dppf91%
90º
Br2
49%[8]CPP
3 steps25% yield
approach towars the synthesis of uniform CNTs– 1.armchair CNT1-1. Bertozzi's strategy; JACS. 2008, 130 , 17646.
2. chiral CNT; Nat. Commun. 2011, 2:492.Hex
Hex
XX
X = BrX = Bpin
Miyauraborylation
91%
PtCl2(cod)CsF
74%
Hex
HexHex
Hex
Pt(cod)
Pt(cod)
Hex
Hex
(cod)Pt
(cod)Pt
Hex
Hex
PPh3
94%(6 isomers)
Hex
Hex
Hex
Hex
Hex
3.zigzag CNT: ???
CPP
CC
smaller ring size=> narrower HOMO-LUMO gap[5]CPP has smaller gap than OPP
small ring-size CPPs exhibitsstrong polyene like character
CPPsOPPs
JACS. 2011, 133 , 8354.
H2N
AcHN NHAc
NH2
1. NaNO2 HCl2. H2SO4
HN
NNN
N
HN
NN
NNN
NH2N
NH2
H2NOSO3H
24%+ 48% mono NH2+ di NH2 isomers
furanePb(OAc)4
THF, reflux79%
anti/syn = 77:23
OO
JOC, 1986, 51, 979
TCI[5]CPP.....¥39,000/ 20 mg[12]CPP...$1209.00/ 10 mg
Chem. Sci., 2015, 6, 2746.
high templow temp
Chemistry of π-extended Molecules Baran lab Group Meeting5/7/16
cycloacene(not yet made!!!)
Yuzuru Kanda
OO
O
COOMeCOOMe
CuCl2, Pd/C
CO, MeOH92%
O
COOMeCOOMe
MeOOCMeOOC
1. LAH2. SOCl2, py3. KOtBu
O
Helv. Chem. Acta. 1980, 63, 1149.ACIE, 1987, 26, 892.TL, 1996, 37, 1983.TL, 1996, 37, 1987.
2 X D.A.
OO
OO
O O
1. TiCl4, LAH2. Ac2O, HCl
cyclacenes
O O
OO
O
O O
O
Hex
Hex
Hex
Hex Hex
HexHex
Hex
PCC
O
O O
O
Hex
HexHex
Hex
O
O
Graphene, 2D molecules
O
Ph
PhPh
Ph
PhPh
Ph
Ph Ph2
Ph
PhPh
Ph
Co3(CO)8
dioxane5 d, 100 ºC
71%
AlCl3CuOTf
CS2???%detected by TOF-MStoo broad signal to prove
"superacene"C222H42
M = 2709
ACIE, 1997, 36, 1603
Ar Ar
OH
I
Br Ar Ar
OMe
PhPhCAN
MeOHrt
quant1. LiNaph; Ar2CO
2. BF3•Et2OAr Ar
Ph
ArAr
Phe–
LiAr Ar
Ar Ar
H
HHHH
H
inperfectconjugation
SiHR2
SiHR2
LiNaph; I2
SiHR2
SiHR2 Si
Si
R R
R R
JACS. 2003, 125 , 13662X
Y
R R
R R nother examplesX, Y = B, C, N, Si, S, P
Helicenes: the first helicene was synthesized by R. Weitzenbock in 1918
2
1. hν, I2 propylene oxide 90 ºC, 48 h, 7%
2. TBAF3. Tf2O, py4. Pd(OAc)2, Et3N HCOOH10% (3 steps)
TIPSO
[16]heliceneknow to form< 1% isomer
ACIE. 2015, 54, 6847.
N O
COOHMe
NO2
NO2NO2
O2N
δ- δ+NO
COOHMe NO2
NO2
NO2O2N
racemic
(+)-[6]helixene
CT-complex
Chiral resolution; JACS. 1955, 77, 3420. JACS. 1956, 78, 4765.
repeat unitn: upto 6
COPVn; JACS. 2012, 134 , 19254.
RR
RR
R
RCT complex
formation
✔ R = Me✘ R = Et
Chemistry of π-extended Molecules Baran lab Group Meeting5/7/16
Yuzuru Kanda
OTBDMS
OTBDMS O
OS
O
p-Tol
DCM
–40 to –20 ºC51%
e.e. > 98%dearomatizedto increase reactivity
TBDMSO
OTBDMS
O
O
TBDMSO
OTBDMS
O
O
O
O
O
O
(P)
(M)
H
CAN60%
92% ee
DDQ88%
96% ee
O
MeO
HO
MeO
Me
Me
Me
O
OMe
Me
KHMDS18-crown-6
(1R, 4S) > 98% ee(1S, 4R) > 83% ee
MeOAc
Me(P) > 98% ee(M) > 83% ee
enantiodivergent approach; Chem. Comm. 2002, 1412.
oxy-Cope approach; TL, 2003, 44, 2167.
N MeMe
IN MeI
OH
Ph
Me 1. tBuOH2. MeI
PhMe
O
nBuLi
87%
(P)-[5]helicenesynthetic applicationJACS. 2010, 132 , 4536.
NH
NH
NHN
H
TFPB
1. (2 mol%)
2. benzoquinone
NO2R'
NMe
NH
Me
NO2
NMe
MeO
R69%
90% ee
NHEt
Et
Ph NO2
Ph
NO270%20% ee
55%70% ee
3D carbon material: diamond, carbon nanohorn, junction of CNTs etc...
Stella BPM 3709380,000 times heavier
than the earth
nanodiamond
nano-particlefluorescentlow toxicityhigh stability
NDNDair
425 ºC5 h
1. SOCl22. NH2R
ND support synthesis; JACS. 2009, 131 , 4594. JACS. 2006, 128 , 11635.
NDNHR
OO
OH
ND NH
ON3
ND NH
ON
N N
R
R = alkyl, FcHN
O
MeCN
))), 30 min
Cl2,hνND ClNH3, Δ
ND NH2
Chem. Eur. J. 2008, 14 , 1382.
OSi
RO ORNH
GlyPheGlyPhe OSi
RO ORNH
O
S
NH
NH
O
H
H
PhO
Ph
Me
Me
Me
Me
TIPS
TIPS
Me
Me
Me
MePh
Ph
G
GG
G
GG
GG
GG
GGG
GG
G
G
G GG
GGG
GG
GG
G GG
G G
1. o-xylene, reflux2. TBAF
other examples
pushing the synthetic limit...; ACIE, 2005, 44, 6348.
repeatthe cycle
22 nmC10113H9028Si128M = 134162
Chemistry of π-extended Molecules Baran lab Group Meeting5/7/16
Stevens rearrangement approach; JACS. 1994, 116, 5084.