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Казанский национальный исследовательский технологический университет

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Negishi E. 2002 Handbook of organopalladium chemistry for organic synthesis / 0863 942

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[214]

[215]

LiCl NMP

PPh CO

PPh

AsPh

(dba)

CN NCH

OMe

MeO

SnMe

SnBu

OTIPS

tBuO

TMS

(−)-strychnine

manoalide

seco-manoalide

		O
N	H
		H
		N
		O

O O

−)-strychnine
(
	O			O	OH


jatrophone	CHO				OH	seco-manoalide
(+)−-
(+)−-		O		OH
O		O


-			O
(+)-(2′S,3R) zoapatanol			HO			manoalide

O Me	Me	OH	O OH Me oleandolide
O Me	Me	OMe	O OH Me oleandolide
O	OH Me
	OH Me

(Continued )

923

TABLE 9. (Continued )

Catalyst Additive Yield (%) Reference

R′X

Name

n C

[76],[77]

TlOH

4 ) 3 Pd(PPh

O TMSOBn (cf. [76])

O I 28 (−)-chlorothricolide TBDPSO B

[78]

TlOH

4 ) 3 Pd(PPh

OTBDPS

Br	Br
	2
	B(OH)

28 (−)-chlorothricolide HO

3 CH

[79],[80]

[216]

TlOH

)

Pd(PPh

)

Pd(PPh

OMe O

OCH

I OCH

TMSOMOM

ClOC

MeO

riccardinB

ZnBr

B(OH)

MeO

(−)-chlorothricolide

riccardinB

924

[87]

[88]

[217],[218]

77−86

TlOH

NEt

Pr-i

)

PdCl(PPh

)

CHCl

(dba)

PhCH

Pd(PPh

OTBS

OtBu

O O

OTBS

Br TBDPSO

ClOC

OPiv

B(OH)

H H

SnBu

TMS

PMBO

indanomycin

kijanolide

(cf.[88])

spinosynA

	−[109]
	[105]
	82
	LiCl
	4
	)
	3
	Pd(PPh
	OTf
H	O
H	H
	H
	MEMO
	3
	SnBu

brevetoxinA	(cf.[105])
49

	OMe
OMe	Me	O Me
OMe	O	O
		O
			H
		H		A
		H		A
O		O O	H	spinosyn
	O		O
	O
	Me
N
	2
Me

N H		H
	H	H
Me O	H	indanomycin
	O
	H O
	Me	HO

925

III.2.13)(cf.

OrganometalsSubstituted

-Hetero-

-Cross InvolvingCoupling

10.TABLE

Catalyst Additive Yield (%) Reference

R′X

Name

n C

[42],[43]
75
DIBAH
2
)
3
Pd(PPh
2
Cl
		OMOM
OMOM

I
OTBS		O ZnCl
OTBS		O ZnCl
TBSO
vineomycinone	B2methylester
26

[123]	[123]
15	19

machicendiol

)

Pd(PPh

OMe

egonol

(+)

−

H OH

R= R=

ZnCl

OH CO

O OMe

O OH

vineomycinoneB2

OTBS

methylester

OH HO

egonol

MeO

−machicendiol-(+)TBDPSO

TBDPSO

926

III.2.14)(cf.

CompoundsSubstituted

-Hetero-

-Cross InvolvingCoupling

11.TABLE

Catalyst Additive Yield (%) Reference

R′X

Name

n C

[135]

NH 2 CuI Pr -i

2 ) 3 Pd(PPh 2 Cl

O		O	OTBS


	I

11 (+)-harveynone

[136]		[136]
62		74
CuI	N	CuI
CuI	Et	CuI
	3

2 Pd(OAc)

OMe	O
MeO		O



I

11 (+)− -harveynone

2 ) 3 Pd(PPh 2 Cl

		O
O			OH


	I
3
		SnBu	OTMS

11 (+)− -harveynone

[219]

[220]

BuLi

nakienoneB

Pd(TFP)

)

Pd(PPh

HO HO

nakienoneA

TBSO

ZnBr

OTMS ZnBr

OTBs

TBSO

harveynone

nakienoneA

nakienoneB

(+)-

(Continued )

927

TABLE 11. (Continued )

Catalyst Additive Yield (%) Reference

R′X

Name

n C

[135]
54
	NH
CuI	2
CuI	i-Pr
2
)
3
Pd(PPh
2
Cl

O		O	OTBS
O			OTBS
	I

18 (−)-tricholomenyn A

[54]	[54]	[54]	[140]		[221]
72	65	70	94		90
			CuI piperidine
4	4	4	4		4
)	)	)	)		)
3	3	3	3		3
Pd(PPh	Pd(PPh	Pd(PPh	Pd(PPh		Pd(PPh
Br	Br	Br	Cl			O O
Br	Br	I				O O
I	I	I	Cl			O
				Br		CO
					3
						H
ZnBr	ZnBr	ZnBr	C	ZnCl
			11
			H
			5
			HO



		TBS		O		O
xerulin			(5S,12S)-DiHETE		gadain
18			20		20

O	gadain
O

	O
		COOH
			HO	DiHETE
				S)-
				S,12
HO	11			S,12
HO			C	(5
			H
	5
		O
	O
				xerulin
				xerulin

	O
O		OAc	tricholomenynA





			(−)-

928

[61]	[62]	[222]	[221]
61	58	80	81

4	4
)	)
3	3
Pd(PPh	Pd(PPh
Cl	Br
Cl		Br


3	ZnCl
SnBu
OH	OH
lipoxinB	(2E,6E,8E)-N-(2-methyl- propyl)-2,6,8-hexadecatrien- 10-ynamide
20	20

)

Pd(PPh

TIPSO

O O

SnBu

ZnCl

TIPSO

miroestrol	savinin
20	20

			O
			O
O	O		savinin
	O

		O
		O

H OH	H	H O	OH miroestrol
OH	H
	H
	O

O	N		(2E,6E,8E)-N-(2-methyl- propyl)-2,6,8-hexadecatrien- 10-ynamide
		11


		H
		5
		C
COOH		OH
OH		HO	lipoxinB

(Continued )

929

TABLE 11. (Continued )

Reference		[223]
Yield(%)		84
Additive		BuLi
		2
Catalyst		Pd(TFP)
Catalyst		Cl
		2
		11
X′	OTBS	H
X′	OTBS	C
		5
R
		I
	ZnBr	OTMS
RM

			4
			)
			2
			THPO(CH
Name		carbacyclin
		(+)−-
n		21
C		21

47 [224],[225]

4 ) 3 Pd(PPh

3 OCH

Br O

3 SnMe

epolactaene-(+) TBDPSO

[226]

CuI

2 CN) 3 Pd(CH 2 Cl

OMPM

3 SnBu

CO 3 H

21 (+)-epolactaene

TFP 62 [227]

3 (dba) 2 Pd

OMe

O I

ZnBr

TBSO

21 (+)-epolactaene

70 [94]−[97]

2 CN) 3 Pd(CH 2 Cl

3
O		OCH		OSEM

	I
	I
		OPMB		SnBu
				3
				PMBO
			(+)-zaragozicacidA
35

11 H 5 C

	OAc				Me


	OH				O COOH
	O			O		OH
O	O	Me HOOC HOOC				OH


		Me
	O		OMe

O		O


O		O

	OH
H	H
	3
	)
	2
	HOOC(CH

(+)-zaragozic acid A

(+)-epolactaene

( )-carbacyclin

930

TABLE 12. Conjugate Substitution (cf. III.2.15)

Catalyst Additive Yield (%) Reference

R′X

Name

n C

[136]

[137]

[192]

CuI

CuI Et

PPh

DIBAH

)

Pd(PPh

Pd(OAc)

MeO I O

BrCOOH

OMe

OTBS

ZnBr

(+)

dendrolasin

goniobutenolide

harveynone-

−

[120]
50
CuI	N
CuI	Et
	3
4
)
3
Pd(PPh
	COOH
	I

15 freelingyne

[54]

xerulin

CuI Et

BHT

)

dendrolasin

Pd(PPh

COOH

freelingyne

goniobutenolideA

OH O

xerulin

harveynone

(+)-

(Continued )

931

TABLE 12. (Continued )

Reference	[199],[200]			[148]
Yield(%)	77			70
Additive		K			CuI
	3
		CO
	2
				2
		Pd(dppf)		)
		Pd(dppf)			Pd(PPh
				3
Catalyst		Cl			Cl
	2			2
	3
		OCH	O
R′X
		Br


			Br
				AcO
RM		B	OAc
		B


		S	Br


		S		AcO
Name		(+)−-dihydroxy- serrulaticacid			rubrolideA
C	20			21
n

	[148]
	54
N	CuI
Et	CuI
3
	2
	)
	3
	Pd(PPh
	2
	Cl

COOH
I
Br
Br	AcO
Br Br



	AcO
		rubrolideC

	[148]			[148]
	54			50
N	CuI	N			CuI	N
Et	CuI	Et			CuI	Et
3		3				3
	2			2
	)			)
	3			3
	Pd(PPh				Pd(PPh
	2			2
	Cl				Cl
COOH			COOH I			COOH I
	I Br
	AcO		Br	AcO

AcO	AcO
rubrolideD	rubrolideE

	Z
	Y
	X
	R
	Rubrolides diacetates
	Z
Y
RO	Y

COOH HO

H H H H
Br H Br H
Br Br H H
Ac Ac Ac Ac
A C D E
O
	O

			X


		X	RO

(+)− -dihydroxy- serrulatic acid

932

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