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

[75]		[76],[77]	[78]	[79],[80]
44		74	72	86
TPPTS	NH	TlOH	TlOH	TlOH
	Pr-i
	2
2		4	4	4
		)	)	)
Pd(OAc)		Pd(PPh	Pd(PPh	Pd(PPh
		3	3	3

				OMe
				O	I	TMSOBn	Br
I
						O
O B O
					O B
				OR		TBDPSO
	myxalamideA					(−)-chlorothricolide	(cf.[77])
26						28

	3
OTBDPS	OCH
	3
	CH

Br

2 B(OH)

HO 28 (−)-chlorothricolide (cf. [78])

3
OCH		OMOM
		TMS
I
2
B(OH)

HO
(−)-chlorothricolide	(cf.[79])
28

		[81]
		71
		DIBAH
		2
		)
		3
		Pd(PPh
		2
		Cl
			O
			N
HO O
			Br

							3
					O			SnBu
H N
O							O H
				O
				−)-manumycinB
				(
				28

				O
				H N							HO
									O
											B
					O						manumycin
H N
O				O				HO			(−)-

NH myxalamide A

OH O

HO

(Continued )

883

TABLE 3. (Continued )

Reference	[82],[83]
Yield(%)	82
Additive	DIBAH
	2
Catalyst	)
	Pd(PPh
	3
	2
	Cl
R′X	OMe
			O
	Br
	Cl
	2
	ZrCp
RM	OR

Name	papulacandinD
n	31
C

[84]		[85],[86]
46	69	27		57
		3
TFP			AsPh
		3
			CHCl
3		.
		3
(dba)			(dba)
2		2
Pd			Pd
Et	Br	Me
CO
2
N		O
OTIPS S	S	N
		O
Br				BocHN
		Me
3			SnBu
SnBu
				3
N			N
2
Me			Me
				2
(−)-pateamineA		(−)-pateamineA
31		31

61 [87]

	4
	)
	3
	Pd(PPh
Me	I
	Me
	H
	O
O	H O
O	Me	HO
	N H	H
	H
	O
	Sn
	3
	Bu
	indanomycin
	31

N H		H
H
Me O	O	indanomycin
	H
	H O
	Me	HO
2
NMe

S	N			O Me	pateamine- A
	O
	O
				O	−)
					(
	Me	N
		H
		2

	OH		*		D
OH	O	HOO	*	OH	papulacandin
HO
	O
	HO O

884

[89],[90]

[88]

[91]

[92]

78

77−86

40

NA

NMP

TlOH

DMF

2

2

CN)

3

4

CN)

4

(CH

)

3

)

2

3

Pd(CH

3

PdCl

Pd(PPh

Cl

Pd(PPh

2

Ph

O

TSE

OH

O O

O H

OTBS

OPMB

HO

CO

OTBS

2

Br TBDPSO

I

I

3

Br

I

SnBu

O

O

OTES

2

3

B(OH)

SnBu

ZnBr

O

HO

N

HO

kijanolide HO

stipiamide

[88])(cf.

dihydroavermectin-22,23

B

discodermolides

aglycon

1b

32

33

33

33

		2
Me Me Me	Me	OHOCONH	OH		discodermolides
	HO	Me		Me
		O		OH
		O		Me
O O		OO OH		O H	dihydroavermectin
				OH
HO					22,23-
		OH
		NH
	O
			HO		stipiamide

aglycon

1b B

(Continued )

885

TABLE 3. (Continued )

Catalyst Additive Yield (%) Reference

R′X

RM

Name

n C

		[93]			[93]
		79			84
		DMF
		2			2
		CN)			CN)
		3			3
		(CH			(CH
		2			2
		PdCl			PdCl
OTBS O		OMe	O	OH	NMe	HO
				O
				CH		O
				2
						OH
I					I
3					3
SnBu					SnBu
N		O			FmocN
		neooxazolomycin
		34

70 [94]−[97]

2 CN) 3 Pd(CH 2 Cl

O	OMe
I
SEMO
OPMB	SnBu
	3
	PMBO
(+)-zaragozicacidA
35

[98]	[99]
84	51
2
ZnCl

	4
	)
	3
	Pd(PPh
	SEM
	2
	CO
		OTIPS
	I	Cl
		2
		ZrCp
	H	O
		O
Et	O	Bu
Et	O
	reveromycinB	(cf.below)
	36

	4
	)
	3
	Pd(PPh		I
	O
	2		N H
	CO
	TMS H N				NAc
		AcHN
					OMe
O	O		O		OAcOBn
	O
					Sn
					3
					Bu
	onnamideA		(cf.below)
	38

		OAc				Me		A
		OOH					OH
O			Me HOOC HOOC					zaragozic-(+) acid
						O COOH
					O
			Me
		OH		NMe			O
							HO Me
	O		O
			Me				OH
			OH O			N H		neooxazolomycin

N

O

886

[100]

100

2 TFP ZnBr

3 (dba) 2 Pd

I

ZnBr

40 β-carotene TMS

[100]

68

DIBAH 2

ZnBr

2 ) 3 Pd(PPh 2 Cl

Br

I

2 AlMe

	[100]			[100]
	85			82
	2			2
	ZnBr					TFP ZnBr
	4			3
	)
	3					(dba)
	Pd(PPh					Pd
				2
					TMS
	Br
				I
							Br
	2
	AlMe
				2
							AlMe
	γ-carotene
	40

[100]

74

2 TFP ZnBr

3 (dba) 2 Pd

TMS

Br

2 AlMe

[100]

53

2 TFP ZnBr

3 (dba) 2 Pd

Br

2

AlMe

(Continued )

-carotene

-carotene

887

TABLE 3. (Continued )

Catalyst Additive Yield (%) Reference

R′X

RM

Name

n C

[101]	[102]	[103]
69	65	75
DIPEA NMP	NMP	DIPEA

	3
	CHCl
	.
	3
	(dba)
	2
	Pd
O		Bn
O	O N			OTBS
	I
OTIPS	OTES			SnBu
		3
	Me			O
		O
	Et
	(+)-lepicidinA
	41

	3
	CHCl
	.
	3
	(dba)
	2
	Pd
	O			Xp
	OTBS
		I
OTIPS		OTES
				O
		Et
	(+)-A83543A			aglycon
	macrolide			(lepicidin)
	41

	4
	)
	3
	Pd(PPh
I
	O
O
HO O	O	O
	O	Sugar
3	Hg 2
SnBu
O

43 polycavernoside (cf. below)

2 NMe Me

O

Et O MeH O O

OH O		N H
O
H N				NH
	N
	2
	H

				OMe	OMe
H H		O	O		OMe		lepicidinA
		H					(+)-
H
O
		OMe
			H
	O			O
HO				O
	H N
	H
	OH	O		O			A
	Me						onnamide
	O
		COOH
	Me			OH

		H	O Bu	B
O		O		reveromycin
			O
		C
	2		C
		HO	HO
			2

888

				[104]		−[105][109]
				75		82
						LiCl
				4		4
				)		)
				3		3
				Pd(PPh		Pd(PPh
		O			OtBu
		OTBS			Me Me		OTf
							O
	TBS OO				MeMe	H
							H H
	TBS O O				Me Me	2	MEMO
Me		H OTES H			I		SnBu
	H				H	EtB(OH)
				Me			3
	O	O
		H
		TBSO
				rutamycinB		brevetoxinA	(cf.[105])
				44		49

[110]

88

2 CN) 3 (CH 2 PdCl

O		OTBS

I

3 SnBu

NC

calyculins	(cf.below)
50

[111]	[112],[113]
67	59

2	2
)	)
3	3
Pd(PPh	Pd(PPh
2	2
Cl	Cl

	R
			CN
			I
	I
SnBu			3
			SnBu
3
NC			R
(−)-calyculinA (cf.below)			(+)-calyculinA (cf.below)
50			50

75 [114]

2 ) 3 Pd(PPh 2 Cl

OTBS

CHO

I

3 SnBu

CN

calyculinA	(cf.below)
50

(Continued )

889

TABLE 3. (Continued )

Reference			[33]
Yield(%)			65
Additive					DIPEA
			2
Catalyst					Pd(TFP)
					Cl
			2
			O
R′X					O TBS				Sn
						I
									Bu
								3
					O	O O MeO O
					O
						N
RM	TIPSO	MEMO						O TESO
Name					demethoxyrapamycin
n			50
C

59 [115]

2 ) 3 Pd(PPh 2 Cl

I

CN

3 SnBu

R

51 calyculin C

	O
	R	OH
		O
		O	O O MeO
			N	O
HO
	MO		OH
		O	O
O	N		PO
			3
3			O
			2
R			H
N H
OHO	NOH Me
	2
MeO	Me	O	OH	Me
			Me
	Me		HO	O

OH OH OMe

HO O

	1
Me	R
	Me

HO

O		O	Me
Me	H	O	H	Et
		H HOH
	O	H

O
O
O	O
O	Sugar
HO O

H demethoxyrapamycin	OMe rapamycin
R=	R=
A	calyculinC
calyculin	3
=H	=CH
3	3
=H,R	=H,R
2	2
R R
=CN,	=CN,
1	1
R	R

2 R

rutamycin B

polycavernoside

890

[32]

[33]

[33]

42

74

74

DMF

DIPEA

2

CN)

2

2

Pd(CH

Pd(TFP)

Pd(TFP)

3

2

2

2

Cl

Cl

Cl

S

S

OMe O

OMe

O

I

TBS

I

Bu

TBSO

Bu

I

O

Sn

Sn

3

3

OMeO

SnBu

OO

O O MeO O

OO

O O

3

O OMe

N

N

TESO

O

TIPSO

MEMO

O TESO

TIPSO

MeO

O

O

rapamycin

(cf.above)

rapamycin

(cf.above)

rapamycin

(cf.above)

51

51

51

(Continued )

891

TABLE 3. (Continued )

Catalyst Additive Yield (%) Reference

R′X

RM

Name

n C

[34],[35]

[36]

[36]

27

40

40

DIPEA

AsPh

DIPEA

AsPh

DIPEA

3

3

2

3

3

CN)

CHCl

CHCl

3

.

.

Pd(CH

(dba)

(dba)

3

3

Cl

OMe

OH

Pd

Pd

2

2

2

H

Me

O

O

O

HN

OH

Me

H NOMeO H

O

O

O

O

HN

O

O

O

OH

Me

OO

NH

OH

OMeMe Me

NH N O NH

OH

NH N

I I

Me

I

Bu

O

I

SnBu

Me

O

O

Sn

3

O

OO

O3

3

SnBu

I

OTMS

O

Bu

O NH

Sn

3

rapamycin

(cf.above)

sanglifehrinA

(cf.below)

TBSO

51

60

892