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

[40]

[41]

99			43
			2
			ZnCl			LiCl
			2
			)
3			3
			Pd(PPh
4
)
	Pd(PPh		Cl
			2
	Ph
			Br
O			I			C
						2
Cl						MeO
ZnCl			OTBS			SnBu
						3
			TBSO
	(Z)-tamoxifen		lacriminA
26			31

[42],[43]

DIBAH 75

2 ) 3 Pd(PPh 2 Cl

OMOM

OMOM
I
OTBS				O ZnCl
TBSO
vineomycinone		B2methylester
26

			Me
	2
		OH CO
		Me				O OH	vineomycinoneB2 methylester
OH O
OH		O
HO		Me

	O
O		OH								lacriminA
						O			O

2
NMe
O			tamoxifen
Ph			(Z)-

873

TABLE 3. Alkenyl–Alkenyl Cross-Coupling (cf. Sect. III.2.6)

Catalyst Additive Yield (%) Reference

R′X

RM

Name

n C

[44],[45]		[46]
68		91
		DIBAH
2		2
)		)
3		3
Pd(PPh		Pd(PPh
2		2
Cl		Cl
I		OTBS
O		O Ot-Bu
		Br
		Br
		Cl
	SnBu	2
		ZrCp
3
		TBSO
B
didemnenonesAand		lissoclinolide
11		11

[47]

96

4 ) 3 Pd(PPh

OTHP

14 (7E,9Z)-dodecadien-1-yl Cl acetate MgBr

[48]

NaOEt 82

4 ) 3 Pd(PPh

Br

2 B(OH)

16 bombykol HO

OH

bombykol

OAc		yl
		(7E,9Z)-dodecadien-1-	acetate
OH
	O	lissoclinolide
	O
HO		A B
R	O	didemnenone	didemnenone
1	2
	R	OH=
O	HO		2
			H=
		2	R
		H,R	OH,
		= =
		1	1
		R	R

874

[49]			[50]
58			40
CsF
4
)
3
Pd(PPh					Pd(0)
		O
		H	N
	TfO						O
			I
3			ZrCp
SnBu
			Cl
			2
MeOOC
		juvenilehormone			piperovatine MeO
-cecropia
C
16
16			17

	[51]
	73
	TlOH
	4
	)
	3
	Pd(PPh
	OMe
O	SiO
	3
	Et
	I
	2
	B(OH)

17 restrictinol

[52]

NaOH 54

2 ) 3 Pd(PPh 2 Cl

OTBS

Br

2

BThx

18 coriolic acid MeOOC

COOH

OH	coriolicacid

O				OH OMe	restrictinol
N			O
					piperovatine
				MeO
COOMe
				O	cecropia-	hormone
					C	juvenile
			H		-
					16

(Continued )

875

TABLE 3. (Continued )

Catalyst Additive Yield (%) Reference

R′X

RM

Name

n C

[53]

NaOEt 52

4 ) 3 Pd(PPh

			O
	O
			I
	2
			B(sia)
O			BnO
O
	±)-trispordB
	(
	18

[54]

95

DIBAH 2

ZnCl

2 ) 3 Pd(PPh 2 Cl

Br

Cl

2

ZrCp

18 xerulin TBS

88−95 [55]

	4
	)
	3
	Pd(PPh
COOMe	COOMe

OH	OH
	or
	I
	I

	ZnBr	or	ZnBr
11			11
H			H
5			5
C			C
	methyl	dimorphecolate
19

[25]

75

N 3 Et

4 ) 3 Pd(PPh

	OTf
Me	TBSO
Sn
3

20 (±)-amijitrienol

	OH	(±)-amijitrienol
COOMe	OH	methyl dimorphecolate
(CH
7
)
2
11
H
5
C
O
O
		xerulin

					O		B
							(±)-trispord
O							HO

876

[56]
31
CsF	LiCl
4
)
3
Pd(PPh
OTf
Br	OH
3
SnBu
HO
(±)-aplysiadiol
20

	[57]
	72
	DMF
	2
	CN)
	3
	Pd(CH
	2
	Cl
	I
OH	O		O

3 SnBu

11 H 5 C

20 ascidiatrienolide

	[58]			[59]
	55
	TlOH			100
	4			4
	)			)
	3			3
	Pd(PPh			Pd(PPh
	COOMe
	3
	)
	2
	(CH
			O	O OTf
	I
				3
		B O			SnMe
	O
OTBS		H		TBSO
	11
	5
		C
	(12R)-HETE			(+)-jatraphone
	20			20

							O	(+)-jatraphone
O	O
		COOH
	3
OH								(12R)-HETE
H
	11
		H
	5
		C
	11
		H
	5
		C
OH		O				O		ascidiatrienolide
					OH
Br					OH			(±)-aplysiadiol

(Continued )

877

TABLE 3. (Continued )

Catalyst Additive Yield (%) Reference

R′X

RM

Name

n C

[68]			[69]				[60]							[61]
62			68−76				70							61
	TlOH		LiOH						NaOH
4			4				4							4
)			)				)							)
3			3				3							3
	Pd(PPh		Pd(PPh						Pd(PPh					Pd(PPh
Me			H
			11
2			5
CO			C		OTBS							OTBS	Cl
		OTMS												Cl
							I
		I	I
OTBS O B		O	B(sia)		CO OTBS	OTBS	CO					B(sia)	OH	3	OH
														SnBu
					Me		Me
							2					2
					2
			2
4
							4
	leukotrieneB								leukotrieneB					lipoxinB
20							20							20

[62]

NaOH 23

4 ) 3 Pd(PPh

Br

2 B(sia)

THPO

(2(210 ,6E-2,6,8- E- E,8methyl N-)-ynamide -propyl) - -hexadecatrien

20

O		N				(2E,6E,8E)-N- (2-methyl-propyl)- 2,6,8-hexadecatrien- 10-ynamide
	11
			H
	5
			C
OH	COOH				HO OH	lipoxinB
			COOH
	OH					4
						leukotrieneB
	OH

878

	[63]		[64]				[65]		[66]
	54		86				87		83
					3
		LiCl	KOH		CO				TlOH
					Ag
					2
	2
	)
	3		3				3		3
		Pd(PPh
			4				4		4
			)				)		)
		Cl	Pd(PPh				Pd(PPh		Pd(PPh
	2
OTf		O					OTBS
			O
			H
			H
TBSO			Me O		Br		I		I
		SnBu	B(OH)						2
							Zn 2			B(OH)
			2
	3
			TBSO							HO
	(±)-myrocinC		(11Z)-retinal				vitaminA
	20		20				20

	[67]
	70
	TlOH
	4
	)
	3
	Pd(PPh
	COOMe
OTBS	OTBS
	I

O		11
		H
O B		5
		C

20 (5S,6R)-DiHETE

	COOH
OH			OH			DiHETE
						,6R)-
						(5S
		OH
						vitaminA

CHO (11Z)-retinal

		O OH	C
	OH		myrocin
		H
		O
		Me O	(±)-

(Continued )

879

TABLE 3. (Continued )

Catalyst Additive Yield (%) Reference

R′X

RM

Name

n C

65 [26]

4 ) 3 Pd(PPh

OTBS Br		O
	N	S
	HN
Sn
3
Bu

22 leinamycin

[27],[28]

[70]

86

90

O

H OH

2

CN)

3

O

HN

O

Pd(CH

4

3

)

Pd(PPh

Cl

O

O

HO

2

CHO

TfO

O

NH

O

I

H

H

C N

2

C

Me

MeO

O

O

TBSO

NC

TBSO

Sn

3

3

SnMe

HO

O

+ S O

S −

(±)-8,15-diisocyano-

11(20)-amphilectene

lankacidinC

O

HO

OH

N HN O

S

22

25

lankacidin C

(±)-8,15-diisocyano- 11(20)-amphilectene

leinamycin

880

[29]

64

4 NBu 2 PO 2 Ph

2 CN) 3 Pd(CH 2 Cl

OH I O

3 SnBu

OTBS

( − -) Amacrolactin

24

[29]

82

4 NBu 2 PO 2 Ph

2 CN) 3 Pd(CH 2 Cl

TBSO OTBS I OH

3 SnBu

OPiv

-(+) Emacrolactin

[29]	[30]
42	78
NMP DIPEA	PPh	TlOH
	3
3	2
Pd	Pd(OAc)
(dba)
2
	OAc

	O O			OMeOMe
OTBS							I
	Bu	I	TBS TBSO	OMOM		OTBDPS
	Sn	O
	3
					B
					2
					(HO)
					macrolactinA
					24

I

3 SnBu

OMOM

[30]
58	E
3	macrolactin
AsPh	(+)-
	O
Pd(0)	O
	OH

O

HO

O O

MeO	MeO	(−)-macrolactinA
		O
		O
		OH

HO

HO

(Continued )

881

TABLE 3. (Continued )

Catalyst Additive Yield (%) Reference

R′X

RM

Name

n C

	[71]					[72]
	80					87
			LiCl			LiCl
	4					4
	)					)
	3					3
			Pd(PPh			Pd(PPh
						Me
						2
						CO
						OTf
	TfO
	3					3
		SnBu				SnBu
		dysidiolide				glycinoclepinA
	25					25

	[73]				[74]
	71				71
	TFP		LiCl		TFP			LiCl
	3				3
	(dba)				(dba)
	2				2
	Pd				Pd
OTf		OH			OTf					O
		CH
	2
					Me O Me
Me O Me			O						O
MESO			O	MeO MESO					O
	3				3
	SnBu				SnBu
		O		O	O				O
	(−)-austalideB				(−)-austalideB
	26				26

54 [31]

	2
	CN)
	3
	Pd(CH
	2
	Cl
OMe		NH O			OMe
					I
				O	I
MeO				MeMe
	Me			TBSO	TIPSO
				3
				SnBu
	Sn
	3
	Bu
	(+)-mycotrienol
	26

NH OMe

OMe

mycotrienol-(+)

O

O

HO

HO

Me

O

O

Me

OMe

B

O

austalide-)

Me

Me

O

HO

O

MeO

(−

Me

COOH

COOH

A

OH Me

glycinoclepin

Me

O

O

dysidiolide

Me HO

Me

O

O

Me

OH

882