Palladium-catalyzed domino Heck-disilylation and Heck-monosilylation of alkene-tethered carbamoyl chlorides: synthesis of versatile silylated oxindoles

Abstract

We reported an efficient palladium-catalyzed domino Heck-silylation of alkene-tethered carbamoyl chlorides with hexamethyldisilane. By using this protocol, a variety of mono- and disilylated oxindoles were obtained in moderate to good...

Palladium‐Catalyzed Aryl‐Carbamoylation of Alkene‐Tethered Carbamoyl Chlorides: Access to Diverse Aryl‐Functionalized Oxindoles

“…In recent years, our group [10] realized palladium‐catalyzed cascade cyclization/functionalization of alkene‐tethered carbamoyl chlorides, which opened a new avenue for the synthesis of phosphorylated, [10a] alkenylated, [10b] alkynylated [10c] and silylated [10d] oxindoles. Furthermore, various functionalized spirooxindoles and [3,4]‐fused oxindoles were synthesized via palladium‐catalyzed domino reaction from alkene‐tethered carbamoyl chlorides (Scheme 1a) [10e] .…”

A new synthetic approach to oxindoles (1,3-dihydro-2H-indol-2-ones) by reductive dephosphorylation with hydroiodic acid of 3-(diethylphosphoryloxy)- oxindoles, derived from isatins (1H-Indole-2,3-diones)

“…Oxindoles (1,3-dihydro-2H-indol-2-ones) are a privileged structural motif, which not only occur widely in bioactive natural products and pharmaceuticals [1][2][3][4][5][6] but are also used as synthetic intermediates for various organic transformations [7][8][9][10][11][12]. Many synthetic strategies have been established to access this skeleton, including the oxidation of indoles, [13][14][15] transition metal-catalyzed Heck-type reactions of acrylamides, [16][17][18][19][20][21][22][23][24] metalcatalyzed cyclization of o-haloacetanilides, [25][26][27][28][29] reductive desulfurization of 3-methylthiooxindoles, 30,31 double C-H oxidative coupling of functionalized acetanilides, [32][33][34][35][36][37][38][39] the C-H oxidative radical coupling of acrylanilides, [40][41][42][43] and so on (Scheme 1). Regrettably, all of the aforementioned methods inherently require a specifically functionalized precursor such as the presence of an ortho-halogen, an amino group and the...…”

Palladium-catalyzed Heck-carbonylation of alkene-tethered carbamoyl chlorides with aryl formates

“…In recent decades, palladium-catalyzed domino Heck reactions, 1–10 first reported by Grigg et al . in 1999, 2 have been intensively studied.…”

“…in 1999, 2 have been intensively studied. Considerable progress has been achieved with regard to capturing alkyl palladium species by using a variety of capturing reagents, including halides, 3 cyanides, 4 terminal alkynes, 5 isocyanides, 6 hexamethyldisilane, 7 P(O)H compounds, 8 heterocycles, 9 CO 10 etc . Among them, Heck-carbonylation is a fundamental and promising approach for the synthesis of diverse carbonyl-containing chemicals and it can also prolong the carbon chain.…”