Ruthenium-Catalyzed Oxygenative Transformation of Terminal Propargyl Alcohols to Metheyleneketenes via Allenylidene Intermedia-tes: Synthesis ofα,β-Unsaturated Carboxylic Acid Derivatives

doi:10.6023/cjoc202008044

Abstract

A ruthenium-catalyzed oxygenative transformation of terminal propargyl alcohols to metheyleneketenes via allenylidene intermediates has been developed for the synthesis of a variety of α, β-unsaturated carboxylic acid derivatives. Mechanistic study experiments disclosed that oxygen transfer from pyridine- N-oxide to ruthenium allenylidene generated from the reaction of catalyst CpRuCl(PPh₃)₂/NaBPh₄ with terminal propargyl alcohol resulted in the formation of reactive methyleneketene intermediate, which was trapped into nucleophilic addition reactions to afford α, β-unsaturated product. This reaction offers an attractive complementary strategy to the traditional approach for the synthesis of this class of unsaturated compounds, but in a distinct mechanism, which provides a novel method for the transformation of propargylic alcohols. The metal allenylidene-to-methyleneketene transformation also represents a new mechanistic modality for metal allenylidene-mediated catalysis.

Key words: Keywords ruthenium, allenylidene, propargyl alcohol, oxygen-transfer, methyleneketene, ketene

Cite this article

Xinyu Wang, Qihuan Li, Tingbin Wen. Ruthenium-Catalyzed Oxygenative Transformation of Terminal Propargyl Alcohols to Metheyleneketenes via Allenylidene Intermedia-tes: Synthesis ofα,β-Unsaturated Carboxylic Acid Derivatives[J]. Chinese Journal of Organic Chemistry, 2021, 41(1): 284-296.

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Entry	x/mol%	Addtive	Yield ^b /%
1	10	NaPF ₆ (1 equiv.)	95
2	10	None	Trace
3	None	With or without NaPF ₆	0
4 ^c	10	NaPF ₆ (1 equiv.)	84
5	10	NaPF ₆ (20 mol%)	42
6	10	NaBPh ₄ (20 mol%)	98
7	5	NaBPh ₄ (10 mol%)	85
8 ^d	5	NaBPh ₄ (10 mol%)	97
9 ^d	5	NaBPh ₄ (7.5 mol%)	91

Entry	x/mol%	Addtive	Yield ^b /%
1	10	NaPF ₆ (1 equiv.)	95
2	10	None	Trace
3	None	With or without NaPF ₆	0
4 ^c	10	NaPF ₆ (1 equiv.)	84
5	10	NaPF ₆ (20 mol%)	42
6	10	NaBPh ₄ (20 mol%)	98
7	5	NaBPh ₄ (10 mol%)	85
8 ^d	5	NaBPh ₄ (10 mol%)	97
9 ^d	5	NaBPh ₄ (7.5 mol%)	91

Entry	Catalyst	Additive	Yield ^b /%
1	CpRuCl(PPh ₃) ₂	NaBPh ₄ (10 mol%)	97
3 ^c	[Ru( μ-Cl)(DPPQ) ₂] ₂- [BPh ₄] ₂	None	Trace
2	CpRuCl(dppe)	NaBPh ₄ (10 mol%)	30
4	Other Ru catalysts ^d	NaBPh ₄ (10 mol%)	0
5 ^e	RhCl(PPh ₃) ₃	NaPF ₆ (1 equiv.) or none	0
6 ^e ^, ^f	[RhCl(COD)] ₂	P( p-FC ₆H ₄) ₃ (30 mol%) NaPF ₆ (1 equiv.) or none	0

Entry	Catalyst	Additive	Yield ^b /%
1	CpRuCl(PPh ₃) ₂	NaBPh ₄ (10 mol%)	97
3 ^c	[Ru( μ-Cl)(DPPQ) ₂] ₂- [BPh ₄] ₂	None	Trace
2	CpRuCl(dppe)	NaBPh ₄ (10 mol%)	30
4	Other Ru catalysts ^d	NaBPh ₄ (10 mol%)	0
5 ^e	RhCl(PPh ₃) ₃	NaPF ₆ (1 equiv.) or none	0
6 ^e ^, ^f	[RhCl(COD)] ₂	P( p-FC ₆H ₄) ₃ (30 mol%) NaPF ₆ (1 equiv.) or none	0

钌催化末端炔丙醇经亚丙二烯基卡宾中间体氧化产生亚甲基烯酮: α, β-不饱和羧酸衍生物的合成