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Negishi E. 2002 Handbook of organopalladium chemistry for organic synthesis / 1223 125

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IV.2.2.1

SYNTHESIS OF CARBOCYCLES 1243

Pd(OAc)2

PPh3, Et3N

DMF, 100 °C

PdBr

72%

E = CO2Me

PdBr

PbBr

Pd2(dba)3•CHCl3

P(o-Tol)3, HOAc

PhH, 20 °C, 12 h

78%

PhI, Pd(OAc)2, PPh3, Et3N,

DMF, 100 °C, 12 h

Ph + E

45%

42%

Scheme 14

Pd(PPh3)4, Et3N

MeCN, reflux, 2 h

65%

Scheme 15

B.vi. Synthesis of Cycloheptanes: Cyclization of 2-Halo-1,8-nonadienes

and Related Compounds

Several 7-exo-trig cyclizations of 2-halo-1,8-nonadiene systems have been reported over the last decade; however, a substantial fraction of 8-endo-trig cyclization product has been observed in these cases (Scheme 16, Table 11).

This type of 7-exo-trig cyclization between an iodofurane moiety and a tethered cyclohexenone system served as a key step in the total syntheses of the squalene synthase inhibitors CP-225,917 and CP-263,114 (Scheme 17). Crucial at this point was the fact that the syn- -hydride elimination was essential to install the correct double bond pattern.[62] The formation of cycloheptanes via a 7-endo-trig process might be envisaged as a sequence of a 6-exo-trig, 3-exo-trig, and retro-3-exo-trig process related to the formal 6-endo cyclization. This sequence ought to be the major pathway for disubstituted alkenes as acceptor alkene moieties whereas electron deﬁcient alkenes like , -unsatu- rated ketones are added in the 7-endo mode (Table 12).

1244	IV Pd-CATALYZED REACTIONS INVOLVING CARBOPALLADATION

TABLE 11. Synthesis of Cycloheptanes: Cyclization of Halo-1,7-octadienes and Related Compounds. E CO2Me, E CO2Et

Catalyst, Solvent,

Yield

Starting Material

Product

Temperature

(%)

Reference

Pd(PPh3)2(OAc)2, Et3N,

[61]

THF, 70 °C

OH O

Pd(OAc)2, Et3N, PPh3

[80]

DMF, 100 °C, 12 h

Pd(PPh3)Cl2, Et3N,

[86]

E′

DMF, 100 °C, 7 h

Pd(PPh3)4, Et3N,

[57]

E E

MeCN, reflux, 10 h

Pd(PPh3)Cl2, Et3N,

[86]

DMF, 100 °C, 7 h

			IV.2.2.1	SYNTHESIS OF CARBOCYCLES 1245
TABLE 12. Synthesis of Cycloheptanes: Cyclization of Halo-1,6-octadienes

			Catalyst, Solvent,		Yield
Starting Material		Product	Temperature		(%)	Reference

			PdCl2, Et2NH, Et3N,		68	[38]
			PdCl2, Et2NH, Et3N,		68	[38]
			DMF, 80	C, 8 h
	I		OH



HO
I
			Pd(OAc)2, K2CO3,			[57]
			n-Bu4NCl, DMF, 23 C,		53	[57]
			12 h

“Pd”

7-exo

8-endo

Scheme 16

TBS

(PPh)

Pd(OAc)2 3 2

TBS

EtN,3

dioxane,

100

°C, 24 h

77%

PMBO

TBS = SiMet-Bu

PMB = p-MeOC

H CH

HO 2C

R O

CP-225,917

Scheme 17

1246	IV Pd-CATALYZED REACTIONS INVOLVING CARBOPALLADATION
TABLE 13. Synthesis of Cycloheptanes: Cyclization of 1-Halo-2-(penta-4,5-dienyl)benzene
Derivative: E CO2Et

			Catalyst, Solvent,	Yield
Entry	Starting Material	Product	Temperature	(%)	Reference

•

R = CH2C(CO2Et)2CH2Allyl or CH2C(CO2Et)2(CH2)C≡CMe

•

Bu I

•

			Pd(PPh3)2Cl2,
			(n-Bu)4NCl,
			K2CO3, DMF,
			K2CO3, DMF,
			120 8C, 4 h
			120 8C, 4 h
			E
	E
R
			Pd(PPh3)2Cl2,
			(n-Bu)4NCl,
		E	K2CO3, DMF,
		E	120 8C, 4 h
	E		120 8C, 4 h
	E

E E

		Pd(PPh3)2Cl2,
		(n-Bu)4NCl,
		K2CO3, DMF,
	E	110–120 8C, 4 h
	E
	E
O
		Pd(PPh3)2Cl2,
		(n-Bu)4NCl,
		(n-Bu)4NCl,
		K2CO3, DMF,
		K2CO3, DMF,
	E	110–120 8C, 4 h
	E
		Pd(PPh3)2Cl2,
		(n-Bu)4NCl,
		K2CO3, DMF,
		120 8C, 22 h
	E
	E
		Pd(PPh3)2Cl2,
		(n-Bu)4NCl,
		(n-Bu)4NCl,
		K2CO3, DMF,
		K2CO3, DMF,
	E	120 8C, 4 h
	E

Pd(PPh3)2Cl2, (n-Bu)4NCl, K2CO3, DMF,

120 8C, 3 h

[66]

IV.2.2.1 SYNTHESIS OF CARBOCYCLES 1247

Seven-membered rings are also formed by a Pd-catalyzed 7-exo-trig cyclization of benzyl halides with an ortho-tethered 4 -pentenyl group as reported by Negishi and coworkers (Scheme 18).[16]


Cl		Pd(PPh3)4, Et3N
	MeCN, reflux, 6 h
	MeCN, reflux, 6 h
E	64%		E
	64%
		E = CO2Et
		E = CO2Et	E

Scheme 18

B.vii. Synthesis of Cyclooctanes: Cyclization of 2-Halo-1,8-decadienes

and Related Compounds

In their studies toward the total synthesis of Taxol®, Danishefsky and co-workers have focused their attention on the formation of eight-membered rings by an intramolecular Heck reaction proceeding by an 8-exo-trig cyclization of a 2-halo-1,8-decadiene system (Scheme 19, Table 14).

X	“Pd”		+
		8-exo
			9-endo
		Scheme 19

B.viii. Synthesis of Cyclononanes and Larger Ring Systems: Cyclization of 2-Halo-1,n-decadienes and Related Compounds

The possibility of forming cyclononanes and larger rings by Pd-catalyzed intramolecular cross-coupling reactions has been investigated to a far lesser extent than that of the smaller rings. Very good yields have been reported for the cyclization of 2-bromo-1,8,9- trienes in which allenyl groups serve as terminators and/or with the aid of high dilution techniques (Scheme 20, Table 15).

Br	“Pd”
		9

•

9-endo

Scheme 20

1248

IV Pd-CATALYZED REACTIONS INVOLVING CARBOPALLADATIONS

TABLE 14. Synthesis of Cyclooctanes: Cyclization of 2-Halo-1,8-nonadienes and Related

Compounds

Catalyst, Solvent,

Yield

Entry

Starting Material

Product

Temperature

(%)

Reference

Pd(OAc)2, K2CO3,

[61]

80 C, 46 h

OSiEt3

Pd(PPh3)4, K2CO3,

[65]

MeCN, 90 C, 72 h

OTf

Pd(PPh3)4, K2CO3,

[60]

O O

MeCN, MS, 90 C

O O

R = SiMe2t-Bu

TABLE 15. Synthesis of Cyclononanes and Larger Rings: Cyclization of 2-Halo-1,9,10-

decatrienes and Related Compound: E CO2Et

Ring

Catalyst,

Yield

Ref-

Solvent,

Entry

Starting Material

Product

Size

Temperature

(%)

erence

Br		•
		•
		5
Br
	3	•
	3
E
E
I	•
	6
I	•
	7

			Pd(PPh3)2Cl2,
9		9	(n-Bu)4NCl,	55	[66]
9		9	K2CO3, DMF,	55	[66]
			K2CO3, DMF,
			120 8C, 12 h
			Pd(PPh3)2Cl2,
			Pd(PPh3)2Cl2,
	E	9	(n-Bu)4NCl,	62	[66]
			(n-Bu)4NCl,
			K2CO3, DMF,
9			K2CO3, DMF,
9	E		120 8C, 12 h
	E		120 8C, 12 h
			Pd(PPh3)2Cl2,	47
			Pd(PPh3)2Cl2,
			(n-Bu)4NCl,
10		10	(n-Bu)4NCl,	(E/ Z =	[66]
10		10	K2CO3, DMF,	(E/ Z =	[66]
			K2CO3, DMF,	73:27)
			120 8C, 12 h	73:27)
			120 8C, 12 h
			Pd(PPh3)2Cl2,


11		11	(n-Bu)4NCl,	40	[66]
11		11	K2CO3, DMF,	40	[66]
			K2CO3, DMF,
			120 8C, 12 h

	IV.2.2.1	SYNTHESIS OF CARBOCYCLES			1249
TABLE 15. (Continued)

			Catalyst,
		Ring	Solvent,	Yield	Ref-
Entry Starting Material	Product	Size	Temperature	(%)	erence

		Br
		Br			•
5
	E					E
		E	4	E
Bu I

				•
6
6	E				E
	E				E
		E	4	E

E E

E E Bu

E E

26 O

Pd(PPh3)2Cl2,

12 (n-Bu)4NCl, 50 [66] K2CO3, DMF,

120 8C, 12 h

Pd(PPh3)2Cl2,

12 (n-Bu)4NCl, 27 [66] K2CO3, DMF,

120 8C, 12 h

Pd(OAc)2, EtNiPr2, LiCl,

13/26 (8 mmol L21) 61/17 [4] DMF, 80 8C,

2 d

BuI

•

12 E

•

12 E

			E	E	Pd(PPh3)2Cl2,
					Pd(PPh3)2Cl2,
		20		20	(n-Bu)4NCl,	86	[66]
					(n-Bu)4NCl,
					K2CO3, DMF,
					K2CO3, DMF,
			E E	9	120 8C, 12 h
			E E
			E	E	Pd(PPh3)2Cl2,
Bu					Pd(PPh3)2Cl2,
				20	(n-Bu)4NCl,	47a	[66]
			12	20	(n-Bu)4NCl,	47a	[66]
				9	K2CO3, DMF,
			E	9	120 8C, 12 h
					120 8C, 12 h

				E E	Pd(PPh3)2Cl2,
	21			21	(n-Bu)4NCl,	66	[66]
				21	(n-Bu)4NCl,	66	[66]
					K2CO3, DMF,
					K2CO3, DMF,
			E E	8	120 8C, 12 h
			E E

(Continued)

1250

Pd-CATALYZED REACTIONS INVOLVING CARBOPALLADATION

TABLE 15. (Continued)

Catalyst,

Ring

Solvent,

Yield

Ref-

Entry

Starting Material

Product

Temperature

(%)

erence

Size

Pd(PPh3)2Cl2,

(n-Bu)4NCl,

[66]

K2CO3, DMF,

120 8C, 12 h

12 E

E E

Pd(MeCN)2Cl2,

[68]

Et3N, MeCN,

25 8C, 11 h

aYield determined by NMR spectroscopy with an internal standard.

C. SYNTHESIS OF BICYCLIC SYSTEMS

C.i. Cyclization of 8-Substituted 6-Halo-1,6-octadienes and Related Compounds with an Additional Leaving Group

Starting from 6,8-disubstituted 1,6-octadienes having two leaving groups in a 1,3- relationship, Pd-catalyzed cyclization leads to the formation of bicyclic vinylcyclopropanes (Scheme 21).[78] The insertion of palladium into the vinylic carbon–halogen bond is regarded as the ﬁrst step. The thus formed intermediate might rearrange to a palladium–carbene complex, which in turn cyclopropanates the other double bond. Alternatively, the alkenylpalladium halide carbopalladates the other double bond and a 3-exo-trig cyclization with subsequent elimination of a palladium(II) salt follows up to form the bicyclic system. Besides bromoallyl esters, propargyl carbonates with an alkenyl tether can also serve as starting materials; however, the presence of sodium formate and Et4NBr is required to suppress the formation of dehydrodimers (Table 16). Propargyl carbonates have also been used in a domino carbocyclization–methylation sequence by means of zincates as nucleophiles (Sect. IV.3.2).

Similar approaches to ethenylcyclopropanes from open-chain halodienes or haloenynes have been published by the groups of Oppolzer and Grigg. However, these cascades proceed with a different termination (zincates).[80]–[82]

E		“Pd”
Br			E
Br			E
E			E
			E
	X
		Scheme 21

				IV.2.2.1	SYNTHESIS OF CARBOCYCLES	1251
TABLE 16.			Synthesis of Bicyclo[3.1.0]hexanes: Cyclization of 6-Halo-1,6-octadienes and 1,6-
Octenynes[78]

					Catalyst, Solvent,	Yield
	Entry	Starting Material		Product	Temperature	(%)

1		E	Br	E	Pd(OAc)2, PPh3, Et3N,	22–34a
				E
		E		E	MeCN, 85 C, 5–6 h

E = CO2Me

X = OAc, OCOCF3, OCO2Et

Pd(OAc)2, PPh3, Et3N,

NaO2CH, Et4NBr,

OCO2Me

MeCN, 85

C, 2 h

E = CO2Me

Pd(OAc)2, PPh3, Et3N,

MeCN, 85

C, 1.5 h

OCO2Me

E = CO2Me

aThe influences of different bases and ligands lead to byproducts and different product compositions.

D. OTHER METHODS

Intramolecular Heck reactions leading to carbocycles involving domino, tandem, or cascade reactions terminated with tethered alkenes and other nucleophiles will be covered in Sect. IV.3.1 and V.3.2, respectively.

E.SUMMARY

1.Various ring sizes (4 to 21 carbon atoms) have been achieved by intramolecular Heck reactions.

2.All formations of fourand ﬁveas well as most of the 6-membered rings proceed via an n-exo-trig carbopalladation, while the formation of larger rings has mostly been achieved by n-endo-trig processes.

REFERENCES

[1]S. Bräse and A. de Meijere, in Metal-Catalyzed Cross Coupling Reactions, (F. Diederich and P. J. Stang, Eds.), Wiley-VCH, Weinheim, 1998, 99–166.

1252	IV Pd-CATALYZED REACTIONS INVOLVING CARBOPALLADATION

[2]A. de Meijere and S. Bräse, J. Organomet. Chem., 1999, 576, 88–110.

[3]M. Hiroshige, J. R. Hauske, and P. Zhou, J. Am. Chem. Soc., 1995, 117, 11590.

[4]G. Dyker and P. Grundt, Eur. J. Org. Chem., 1999, 323.

[5]F. E. Meyer, J. Brandenburg, P. J. Parsons, and A. de Meijere, J. Chem. Soc. Chem. Commun., 1992, 390.

[6]F. E. Meyer, P. J. Parsons, and A. de Meijere, J. Org. Chem., 1991, 56, 6487.

[7]F. E. Meyer, H. Henniges, and A. d. Meijere, Tetrahedron Lett., 1992, 33, 8039.

[8]R. Grigg, V. Sridharan, and S. Sukirthalingam, Tetrahedron Lett., 1991, 32, 3855.

[9]N. E. Carpenter, D. J. Kucera, and L. E. Overman, J. Org. Chem., 1989, 54, 5846.

[10]S. Bräse, Synlett, 1999, 1654.

[11]H. Iida, Y. Yuasa, and C. Kibayashi, J. Org. Chem., 1980, 45, 2938.

[12]R. Grigg, P. Fretwell, C. Meerholtz, and V. Sridharan, Tetrahedron, 1994, 50, 359.

[13]R. Yoneda, Y. Sakamoto, Y. Oketo, K. Minami, S. Harusawa, and T. Kurihara, Tetrahedron Lett., 1994, 35, 3749.

[14]R. Grigg, V. Sridharan, P. Stevenson, S. Sukirthalingam, and T. Worakun, Tetrahedron, 1990, 46, 4003.

[15]T. J. Katz, A. M. Gilbert, M. E. Huttenloch, G. Min-Min, and H. H. Brintzinger, Tetrahedron Lett., 1993, 34, 3551.

[16]G.-z. Wu, F. Lamaty, and E. Negishi, J. Org. Chem., 1989, 54, 2507.

[17]M. Toyota, Y. Nishikawa, and K. Fukumoto, Tetrahedron Lett., 1994, 50, 6495.

[18]M. Toyota, Y. Nishikawa, and K. Fukumoto, Tetrahedron, 1994, 50, 11153.

[19]S. Bräse, J. Rümper, K. Voigt, S. Albecq, G. Thurau, R. Villard, B. Waegell, and A. de Meijere, Eur. J. Org. Chem., 1998, 671.

[20]R. Grigg, P. Kennewell, A. Teasdale, and V. Sridharan, Tetrahedron Lett., 1993, 34, 153.

[21]J. M. Tour and E. Negishi, J. Am. Chem. Soc., 1985, 107, 8289.

[22]F. E. Meyer, K. H. Ang, A. G. Steinig, and A. de Meijere, Synlett, 1994, 191.

[23]K. H. Ang, S. Bräse, A. G. Steinig, F. E. Meyer, A. Llebaria, K. Voigt, and A. de Meijere,

Tetrahedron, 1996, 52, 11503.

[24]J. M. Gaudin, Tetrahedron Lett., 1991, 32, 6113.

[25]Y. Zhang, B. O Connor, and E. Negishi, J. Org. Chem., 1988, 53, 5588.

[26]B. O Connor, Y. Zhang, and E. Negishi, Tetrahedron Lett., 1988, 29, 3903.

[27]E. Negishi, Y. Zhang, and B. O Connor, Tetrahedron Lett., 1988, 29, 2915.

[28]S. Liang and L. A. Paquette, Acta Chem. Scand., 1992, 597.

[29]R. Grigg, V. Loganathan, V. Santhakumar, V. Sridharan, and A. Teasdale, Tetrahedron Lett., 1991, 32, 687.

[30]B. Moeller and K. Undheim, Tetrahedron, 1998, 54, 5789.

[31]M. Moren-Manas, R. Pleixats, and A. Roglans, Liebigs Ann. Chem., 1995, 1807.

[32]R. Grigg, R. Stevenson, and T. Worakun, J. Chem. Soc. Chem. Commun., 1984, 1073.

[33]R. Grigg, P. Stevenson, and T. Worakun, Tetrahedron, 1988, 44, 2033.

[34]R. Grigg, P. Stevenson, and T. Worakun, Tetrahedron, 1988, 44, 2049.

[35]R. Grigg, R. Stevenson, and T. Worakun, J. Chem. Soc. Chem. Commun., 1985, 971.

[36]J. W. Dankwardt and L. A. Flippin, J. Org. Chem., 1995, 60, 2312.

[37]S. Lemaire-Audoire, M. Savignac, C. Dupuis, and J.-P. Genet, Tetrahedron Lett., 1996, 37, 2003.

[38]Z. Owcarczyk, F. Lamaty, E. J. Vawter, and E. Negishi, J. Am. Chem. Soc., 1992, 114, 10091.

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