New diphosphine ligand

dcypt[3,4-Bis(dicyclohexylphosphino)thiophene]

Metal-dcypt catalyzed...
Decarbonylative diaryl ether synthesis
O

Metal-dcypt
Catalyst

ArOAr

OAr

Ar

Cyanation of phenol derivatives
with aminoacetonitriles
ZO
Ar

α-Arylation of esters and amides
with phenol derivatives
O
H

Z+R'O
R''

Metal-dcypt
Catalyst

ArO

R

RN

CN

Metal-dcypt
Catalyst

CNAr

Z=t-Bu, NMe2O

Ar

Z
R'R’’=t-Bu, NMe2

Z = R (Ketones)
Z = OR (Esters)
Z = NR2 (Amides)O+

Decarbonylative alkynylation ofaromatic estersO+ HOArSi

Metal-dcypt
Catalyst

ArSiC-H Alkenylation of imidazole
NNR

H +NOO

Metal-dcypt
Catalyst

RNNRRAnd more!!
New diphosphine ligand catalyzing various new reaction
Kanto Chemical Co., INC. launched new diphosphine ligand “dcypt”, which were developed byProf. Itami, Nagoya University, Institute of Transformatibe Bio-Molecules and associate Prof.
Yamaguchi, Waseda University, Department of Applied Chemistry. Dcypt ligand catalyze
various new reactions as described above. This ligand is stable in air and easy to handle.
Cat. No.

Product nameSize

05806-95

3,4-Bis(dicyclohexylphosphino)thiophene05806-65

abbreviation：dcypt
CAS : 1638677-61-8
molecular formula : C28H46P2S200 mg

SPP1g

Some reaction examples catalyzed by dcypt ligand + metal complex
Decarbonylative diaryl ether synthesis reaction
Ni/dcypt or Pd/dcypt complex catalyze decalbonylative diaryl ether synthesis reactionof aromatic aryl ester.

ExampleO

Ni(cod)2 (5 mol%)dcypt (10 mol%)
K3PO4 (1.5 equiv)
toluene150 °C, 18 hArOArOArAr

Some of reaction products
NNONNMeO(69%)

OMe

(80%)

(90%)

NN

O

MeO

N

O

MeN

N

O

MeO

NOMe

NO

NN(65%)

N

N

O

NO

O(72%)O

NMe2O(44%)

MeN

O

N

O
F3C

F
(54%)

O
N

O

N

(75%)

O(29%)

Me(57%)

O

N

N

O

OCF3(54%)

Me(87%)FO

CF3(54%)

O

Me

N

N

(81%)

(91%)

O

OMe

O(80%)

(64%)

O

N

N

OMe

O

(48%)

CN(85%)

MeOMe

MeN

O

F

(77%)

OMe(84%)

NO

O

N(>99%)(50%)(>99%)

O(94%)(69%)

Reference：Decarbonylative Diaryl Ether Synthesis by Pd and Ni CatalysisTakise, R.; Isshiki, R. Muto K.; Itami, K.; Yamaguchi, J. J. Am. Chem. Soc. 2017, 139(9), 3340-3343.

Cyanation of phenol derivatives by using aminoacetonitriles
Ni/dcypt complex catalyze cyanation reaction of phenol derivatives with aminoacetonitriles
as organic cyanating agents. This reaction does not use toxic metal.

Example
t-Bu

O
ArO+O

NiBr2 (5 mol%)dcypt (10 mol%)
Zn (30 mol%)
K3PO4 (2 equiv)
toluene150 °C, 18 hNCNCNAr

Some of reaction products
CNn-But-Bu(65%)

Me(66%)CNMeO
Me2N(61%)(77%) aMePhCN

MeMe(82%) a(78%)

NH
(54%)

CNCN
MeO

OMe

MeO(65%) a(87%)(70%)

NMe(65%)

PhO(63%) a

MeOMeO(81%) a

Me O
CN

CN

CN

CNO

CNO
MeCN

CN

CNO

HH
NC

H

(44%)

NC

OMe
NPhth(69%) aa : NiBr2(10 mol%), Zn(60 mol%), dcypt(20 mol%)

Reference：Cyanation of Phenol Derivatives with Aminoacetonitriles by Nickel Catalysis
Takise, R.; Itami, K.; Yamaguchi, J. Org. Lett. 2016, 18(17), 4428-4431.

Coupling reaction of carbonyl compound with phenol derivatives
Ni/dcypt complex catalyze α-arylation of ketone, ester or amide with phenol derivatives
as arylating agent.

ExampleOO

H

R+t-BuNi(cod)2 (10 mol%)dcypt (20 mol%)
K3PO4 (1.5 equiv)
toluene150 °C, 24 h

Ar
O

R'O

Ar

R
R'

Some of reaction products
O
Ph
Ph(91%)

O

N

O

O

Ph
Ph

(68%)

Ph

O

Ph

Ph(60%)

(71%)

O

OMe

O

Ph

Ph

OMe

O

Ph

Ph (76%)

O

O

O

O
OMe

Ph

O

Ph(57%)

Ph(63%)

O

O

MeO

Ph

Ph
Me(61%)

MeMeMeO(43%)

OO

Me(89%)

Me2N

(81%)

O

F3C

(76%)

ON
Me(76%)

(61%)

O

MeMeN

MeMe(53%)

OMe(73%)

OO(55%)

MeO

MeO

(77%)

O
BnO
NBnN
Met-Bu(79%)

MeO(66%)

O
OMeO

N

MeO

(75%)

O(49%)

NMe(83%)

NMeOMe

MeO

(81%)

OO
O(75%)

O

S(57%)

O

MeOMe

O

O
O

F

MeO

(75%)

OMe
O

t-Bu

(55%)

Reference：Nickel-catalyzed α-arylation of ketones with phenol derivatives
Takise, R.; Muto, K.; Yamaguchi, J.; Itami, K. Angew. Chem. Int. Ed. 2014, 53(26), 6791-6794.
Ni-Catalyzed α-arylation of esters and amides with phenol derivatives
Koch, E.; Takise, R.; Studer, A.; Yamaguchi, J.; Itami, K. Chem. Commun. 2015, 51(5), 855-857.

Decarbonylative alkynylation of aromatic esters

Pd/dcypt complex catalyze halogen-free Sonogashira coupling of aromatic esters withterminal alkynes.

ExamplePd(acac)2 (5 mol%)dcypt (10 mol%)CuI (10 mol%)
Et2NH (4 equiv)
MS3A, 1,4-dioxane
150-170 °C, 16 hO
Ar

SiiPr3H+

O

SiiPr3

Ar

Some of reaction products
N

SiiPr3(59%, 150°C)(63%, 170°C)

NNS

SiiPr3(59%, 160°C)SiiPr3(43%, 170°C)

SiiPr3
N(52%, 160°C)(55%, 170°C)
NN

SiiPr3N

SiiPr3(54%, 150°C)(62%, 170°C)

F3C

N(57%, 160°C)

SiiPr3

O(43%, 160°C)(54%, 170°C)

SiiPrPh

N
S

N(42%, 170°C)
Ph
SiiPr3(57%, 150°C)(74%, 170°C)

F
SiiPr3(53%, 150°C)(55%, 160°C)

3

SiiPr3Ph

S(51%, 150°C)(68%, 170°C)(37%, 170°C)

MeO(60%, 150°C)(87%, 160°C)

SiiPr3(39%, 170°C)

O
SiiPr3

SiiPr3

N(46%, 150°C)(55%, 160°C)

NPh

SiiPr3N

SiiPr3
S(42%, 150°C)

SiiPr3(42%, 160°C)(46%, 170°C)

Reference：Palladium-catalyzed Decarbonylative Alkynylation of Aromatic Esters
T. Okita, K. Kumazawa, R. Takise, K. Muto, K. Itami, J. Yamaguchi, Chem Lett. 2017, 46, 218.

N

C-H alkenylation of imidazoles with enol derivatives
Ni/dcypt complex catalyze C-H alkenylation of imidazoles with enole derivatives in t-amyl
alcohol.

ExampleNN
R

H

Ni(OTf)2 (10 mol%)dcypt (12 mol%)
K3PO4 (3.0 equiv)
t-AmylOH
120 °C, 36 hO+Me 2 NRONNR

R

Some of reaction products
NNNN

NNOMeNN
MeO
N(87%)

(80%)

MeO

NN
MeN
Me(52%)

(86%)

FN

N

N

N

N
MeN
Me(67%)

(87%)

(86%)

ON

N
Me(66%)MeN

N
MeN
Me(75%)(69%)

Me(29%)

Reference： C-H arylation and alkenylation of imidazoles by nickel catalysis: solvent-accelerated imidazole C-H activation
Muto, K.; Hatakeyama, T.; Yamaguchi, J.; Itami, K. Chem. Sci. 2015, 6(12), 6792-6798.

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P

10 g
1g

Ni

5g

KANTO CHEMICAL CO., INC.
REAGENT DIVISION

East Muromachi Mitsui BLDG, 2-1, Nihonbashi Muromachi 2-chome,Chuo-ku, Tokyo, 103-0022, JAPANTelephone+81-3-6214-1092
Telefax+81-3-3241-1053
http://www.kanto.co.jp
E-mail; kanto-61@gms.kanto.co.jp
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