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2.7.2.1.1 Palladium-Catalyzed Cross Coupling of Aryl Halides or Sulfonates

DOI: 10.1055/sos-SD-208-00405

Wu, Y.; Wang, Jun; Kwong, F. Y.Science of Synthesis: Cross Coupling and Heck-Type Reactions, (20132622.

Palladium-catalyzed α-arylation of β-oxo carbonyl compounds has become a useful method for the synthesis of α-arylated carbonyl derivatives. This methodology has many advantages including high turnover numbers (in general in the range 40–96), mild reaction conditions, and good functional group compatibility. Palladium-catalyzed intramolecular arylation of a β-diketone was first reported in 1987.[‌20‌] Since then, an extensive amount of research has been undertaken in this area, and a remarkably active catalyst system for the α-arylation of dialkyl malonates has been reported (Scheme 2).[‌21‌] It was found that sterically hindered alkylphosphines, such as tri-tert-butylphosphine or 1,1′-bis(di-tert-butylphosphino)ferrocene (1), ligate with the palladium center to accelerate the rate of reaction. This system has even been found to be applicable with aryl chlorides, and the method provides a convenient route by which to access α-aryl-substituted carboxylic acids.

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Meeeeeeeeee 8

M8 M Meeeeeee Meeeee Meeee (%) Mee
e-Me Me Me(eee)8 8 88 [‌88‌]
Me Me Me(MMe)8 e-Me8M 88 [‌88‌]

Mee eee ee eeeeeeeee-eeeeee eeeeeeee [Me(MM8)8–MeM ee Me(MMe)8–MeM] ee eeeeeeeee eeeeeeeee eee eee eeeeee eeeeeeeee ee eeeeeeee eeeeeeeeeee eeeee e eeeeeee ee eeee eeeeeeee eee eeee eeeeeeeee (Meeeee 8). Meeeeeee eee eeeeeeee eeeeee eee eeeeeeee, eee eee eeee ee eee eeeeeeeee ee eeeeeeeeee eee eeeeeeeee eeeeeeeeee eeeeeeeeeeee. Me eeeeeeeeee eeee ee eee eeee eeee eee eeeeeeeee eee ee eeeeee eeeeeeeee eeee eee eeeeeeee eeeeeee eee eeeeee eeeeeee eeeeeeeeeee eeee ee eeeeeeee.[‌88‌]

Meeeee 8 Meeeeeeee-Meeeeeeee α-Meeeeeeee ee Meeeeee Meeeeeee[‌88‌]

Meeeeeeeeee 8

Me8 Meeee (%) Mee
8-Mee 88 [‌88‌]
8-MeMM8M8 88 [‌88‌]
Me 88 [‌88‌]
8-MeM8M8 88 [‌88‌]
8-M8MM8M8 88 [‌88‌]

Me eeeeeeeeeee eeeeeeeee eeeeeeee eeeeee eeeee 8-(ee-eeee-eeeeeeeeeeeeee)-8′-eeeeeeeeeeeeee (e-MeMeMeee) eee eeee eeee eeeeeeeee eee eee eeeeeeeee ee eeeeeeee eeeeeeeeeee (Meeeee 8).[‌88‌] Mee eeeeeee, eee eeeeeeeeeee ee eeee eeeeeeeeeeee eeeeeeeee eeeeee eee eeeeeeeee(MM) eeeeeee (8 eee%) eeee eeeeeee eeeeeeee eeeee eeeeeeeee eeeeeeee ee ee ee 88% eeeee. Meeeeeee, eee eeeeeeeee ee 8,8-eeeeeeeee eee eeee eeee eeeeeeee, eeeeeeeee ee eee eeeee eeeeeeeeee eeeeeeeeeeeeee eeeeeeeee-eeeeeeeee eeeeeeee ee eeee eeee.

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Meeeeeeeeee 8

M8 M8 Me8 Meeee (%) Mee
MMe MMe 8-e-MeM8M8 88 [‌88‌]
(MM8)8 8,8-Me8M8M8 88 [‌88‌]
(MM8)8 8-e-MeM8M8 88 [‌88‌]
(MM8)8 8-MeM8MM8M8 88 [‌88‌]

Mee eeeeeeeee ee eeeeeee eeeeeeeeeeeee eeeee ee eeeee eee eeeeeeeeeee ee eee eeeeeeeee ee eeeeeee eeeeeeee eee eeee eeeeeee (Meeeee 8).[‌88‌] Mee eeeeeee eeee eeee eeeeee eeeeeeeee ee eee eeee ee eeeeee, eee e eeeee ee ee ee 888% eee ee eeeeeeee eeee eeeeeeeeeeeeeeeee ee eeee ee eee eeeeeee ee eee eeeeeeee ee eeeeee eeeeeeeeeeeeeeeeeeee(MM) (8 eee%). M eeeeeee eeeeeeeee ee eeee eee eeee eee ee eeeeeee eeee eee eeeeeeee eeeeee ee eeeeee eeeeeeeeee eeee eee eeeeeeee ee eeeeeeee. Meeeeeeeeee, eee eee ee eeeeeeeee eeee eeeeeee ee eee eeeeeeeee eee eeee eeeeeeee eee eeee eeee eeeeeeeee eee eeeee ee eeeee eeee.

Meeeee 8 Meeeee Meeeeeeeeeeeeeeeeeee(MM) Meeeeeeee α-Meeeeeeee ee Meeeeee Meeeeeee[‌88‌]

Meeeeeeeeee 8

M Meeee (%) Mee
Me 88 [‌88‌]
Me 88 [‌88‌]
M 888 [‌88‌]

Mee α-eeeeeeeeeeeee ee eeeeeee eeeeeeeee eeee eeee eeeeeeee ee eeee eeeeeeeee eee eeee eeeeeeee eeeeeeeeeee (Meeeee 8).[‌88‌] Me eee eeeeeeee ee eeeeeeee eeeee eeeeeeeee eeeeeee, eeee ee eee-eeee-eeeeeeeeeeeeee ee (ee-eeee-eeeeeeeeeeeeee)eeeeeeeee eeeeeeeeee 8, eeee eeee eeeeeeee eee eeee eeeeeeeee eeeeeeeeee eeeeeeee-eeee eee eeeeeeeeee eeeeeeee eeeeeeeeeeee eeee eeee eeeeeeeeee eeeeee eeeeeee eeeeeeeee, eeeeee eee eeeeeeeee eeeeeeee 8 ee 88–88% eeeee.

Meeeee 8 Meeeeeeee-Meeeeeeee α-Meeeeeeee ee Meeeeee Meeeeeeee[‌88‌]

Meeeeeeeeee 8

M8 Me8 M Meeeee Meeeeeeeee Meeee (%) Mee
Me Me Me e-Me8M MeM, MMM, 88 °M 88 [‌88‌]
Me 8-M8MM8M8 Me e-Me8M MeM, MMM, 88 °M 88 [‌88‌]
Me Me e-Me8M MeM, MMM, 88 °M 88 [‌88‌]
Me Me e-Me8M MeM, MMM, 88 °M 88 [‌88‌]
Me Me Me 8 M8MM8, eeeeeee, 888 °M 88 [‌88‌]
Me 8-M8MM8M8 Me 8 M8MM8, eeeeeee, 888 °M 88 [‌88‌]
Me Me 8 M8MM8, eeeeeee, 888 °M 88 [‌88‌]
Me 8,8-Me8M8M8 Me 8 M8MM8, eeeeeee, 888 °M 88 [‌88‌]
e-Me Me Me 8 MeM, MMM, 88 °M 88 [‌88‌]
e-Me Me Me 8 MeM, MMM, 88 °M 88 [‌88‌]
e-Me 8-M8MM8M8 Me 8 MeM, MMM, 88 °M 88 [‌88‌]
e-Me 8-M8MM8M8 Me 8 MeM, MMM, 88 °M 88 [‌88‌]
e-Me 8,8-Me8M8M8 Me 8 MeM, MMM, 88 °M 88 [‌88‌]
e-Me Me 8 MeM, MMM, 88 °M 88 [‌88‌]
e-Me Me 8 MeM, MMM, 88 °M 88 [‌88‌]

Mee eeeeeeee ee eeee eeeeeeee eeee α-eeeeee-eeeeeeeeeee eeeeeeeee, e eeeeeeeeee eeeee eeee eee eeeeeeeee eeeeeeeeeeee ee eeeeeeeee eeeeeeeee, eee eeee eeee eeeeeeeee. Mee eeeeeee, eeee eee(eeeeeeeeeeeeeeeeeeee)eeeeeeeee(8)/eee-eeee-eeeeeeeeeeeeee ee eeee ee eee eeeeeeee eeeeee ee eee eeeeeeee ee eeeeee eeeeeee ee eeeeeeeeeeeeeee, ee eeeee ee α-eeee-α-eeeeee-eeeeeeeeeee eeeeeee eeeeeeeee ee eeeeeeee ee eeee eeeeee (Meeeee 8).[‌88‌]

Meeeee 8 Meeeeeeee-Meeeeeeee α-Meeeeeeee ee α-Meeeee-Meeeeeeeeee Meeeeee Meeeeeee[‌88‌]

Meeeeeeeeee 8

Me8 Meeee (%) Mee
Me 88 [‌88‌]
8-MeMM8M8 88 [‌88‌]
8-MeM8MM8M8 88 [‌88‌]
8-e-MeM8M8 88 [‌88‌]
8-eeeeeeee 88 [‌88‌]

Meeeeeeeeeeee, e eee-eee eeeeeeeee ee eeeeeeeeee eeeeeee α-eeee-α-eeeeee-eeeeeeeeeee eeeeeee eeeeeeeee ee eeee eeeeee eeeee eee eeeeeeeeeeeee eeee eeeeeeee eee eeeeeeeeeee eee eeee eeee eeeeeeeee (Meeeee 8).[‌88‌]

Meeeee 8 Meeeeeeee-Meeeeeeee Mee-Mee Meeeeeeee ee α-Meee-α-eeeeee-Meeeeeeeeee Meeeeee Meeeeeeee[‌88‌]

Meeeeeeeeee 8

Me8 Meeee (%) Mee
Me 88 [‌88‌]
8-MeMM8M8 88 [‌88‌]
8-M8MM8M8 88 [‌88‌]
88 [‌88‌]

Mee eeeee eeeeeeee ee eeee eeeeeee eee eeee eeeeeeee ee eee eeeeeeeee ee eee eeee eeeeeee[8.8.8]eeeeee eeee eeeeee ee eeeeeeeeeeeeeeeee (Meeeee 8).[‌88‌] Meee eeeeeeeee, eeeeeeeeee eeeeeeeee eeeee eeee e eeee eeeeeee ee eeeeeeeee(MM) eeeeeee eeee eee-eeee-eeeeeeeeeeeeee ee eee eeeeee ee eeeeeeee eeeeeeeeeeeeee eeeeeee eeeeeeeee ee eeeeee eee eeeeeee eeeeee eeeeeeee ee 88% eeeee.

Meeeee 8 Meeeeeeee ee eee Meeeeee[8.8.8]eeeeee Meee ee Meeeeeeeeeeeeeeee ee Meeeeeeee-Meeeeeeee Meeee Meeeeeee[‌88‌]

Meee eeeeeeeeeeeeeee eee eeeeeeeeee eeeeeeeeee eeeeeeeeeeeee eeeeeeee eeee eeee eeeeeee. Meeeeee, ee 8888, eee eeeee eeeeeee ee Meeeee–Meeeeee eeeeeeee eee ee eeeeeeee eeeeeee eeeeeeee ee eeeeeeeeee eeeeeeeee eeee eeee eeeeeeeeeeeeeeeee, eeeeeeeee e eeeeeeeee(MM) eeeeeee/8-(eeeeeeeeeeeeeeeeeeeee)-8′,8′,8′-eeeeeeeeeeeeeeeeeeee (MMeee) eeeeeee, eee eeeeeeee ee eeeeee eee eeeeeeee ee α-eeeeeeeee ee eeeeeeeee eeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee-Meeeeeeee α-Meeeeeeee Meeee Meee Meeeeeeeeeeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Me8 Meeee (%) Mee
MMe MMe 8-e-MeM8M8 88 [‌88‌]
(MM8)8 8-MeM8MM8M8 88 [‌88‌]

Meeeeeeeeeee Meeeeeeee:

α-Meee-Meeeeeeeeee Meeeeee Meeeeeeee 8 (M8 = Me); Meeeeee Meeeeeeee Meeee Meeeee Meeeeee:[‌88‌]

MMM (8.8 eM) eee eeeee ee e eeeee-eeeeee eeee eeeeeeeeee eeeeeee eeeeeeee (8.88 eeee) ee e eeeeee. MeM (8.88 eeee) eee eeee eeeee eee, eeeee eeeeeeeee ee M8 (ee. 8 eee), eee eeee eeeeeee (8.8 eeee), e-Me8M (8.88 eeee), Me(eee)8 (8.88 eeee), eee eeeeeeeeee MMM (8.8 eM) eeee eeeee. Mee eeee eee eeeeee eeee e eee eeeeeeeeee e MMMM eeeeee eee eeeeeee eeee eee eeeeee. Mee eeeeeee eee eeeeeee ee 88 °M eee eee eeeee ee eeeeeeeeee eee eeeeeeeee ee MM. Meeee eeeeeeee eeeeeeeeee ee eee eeee eeeeee, eee eeeee eeeeeee eee eeeeeeee eeeeeee e eeee ee Meeeee eee eeeeeeeeeeee ee eeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, MM8Me8/eeeeee 8:8) ee eeee eee eeeeeee.

α-Meee-Meeeeeeeeee Meeeeee Meeeeeeee 8 (M8 = Me); Meeeeee Meeeeeeee Meeee Meeeeeeee Meeeeeeee:[‌88‌]

Mee eeeeee 8 (8.88 eeee), Me(eee)8 (8.88 eeee), eee M8MM8 (8.8 eeee) eeee eeeee ee e eeeee-eeeeee eeee eeeeeeeeee eeeeeee eeeeeeee (8.88 eeee) eee eee eeee eeeeeeee (8.8 eeee) ee e eeeeee. Meeeeee (8.8 eM) eee eeee eeeee eee eee eeee eee eeeeee eeee e eee eeeeeeeeee e MMMM eeeeee eee eeeeeee eeee eee eeeeee. Mee eeeeeee eee eeeeeee ee 888 °M eee eee eeeee ee eeeeeeeeee eee eeeeeeeee ee MM. Meeee eeeeeeee eeeeeeeeee ee eee eeee eeeeeeee, eee eeeee eeeeeee eee eeeeeeee eeeeeee e eeee ee Meeeee eee eeeeeeeeeeee ee eeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, MM8Me8/eeeeeee 8:8) ee eeee eee eeeeeee.

References


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