Recent Advances in C(sp3)—H Phosphorylation Based on Secondary Phosphine Oxides and Phosphite Esters

doi:10.6023/cjoc202107044

Abstract

Organophosphorus compounds bearing C(sp³)—P bonds have been widely used in organic synthesis, bioorganic and medical chemistry, agrochemicals, flame retardants and extractants. In recent years, the direct phosphorylation of C—H bonds has received much attention because this strategy represents more straightforward, efficient and atom-economic construction of C—P bonds. The recent advances in C(sp³)—H phosphorylation using secondary phosphine oxides and phosphite esters as phosphorus sources since 2009 are reviewed, and the corresponding reactions are categorized in five types according to the structure of C(sp³)—H bonds.

Key words: secondary phosphine oxide, phosphite ester, C(sp³)—H bond, phosphorylation

Cite this article

Yuanting Huang, Qian Chen. Recent Advances in C(sp³)—H Phosphorylation Based on Secondary Phosphine Oxides and Phosphite Esters[J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4138-4153.

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Entry	Amine	P-Nucleophile	Catalyst	Condition	Yield/%	Ref.
1	R¹, R²=H	R³=OAlkyl	FeCl₂	TBHP, MeOH, r.t.~reflux	57~84	[10]
2	N-Aryl THIQs	R³=OAlkyl	MoO₃	O₂, MeOH, 60 ℃	86~95	[12]
3	N-Aryl THIQs or R¹, R²=H	R³=OAlkyl, Ar		Air, CH₃CN, 50 or 60 ℃	37~94	[13]
4	N-Phenyl THIQ	R³=OAlkyl	NaSbCl₆(α-NaphNO₂), NHPI	O₂, CH₃CN, 40 ℃	81~90	[14]
5	N-Aryl THIQs or R¹, R²=H, alkyl	R³=OMe, OEt	AuNPore	O₂ or TBHP, CH₃CN, 80 ℃	52~90	[15]
6	R¹, R²=alkyl	R³=Ph	[Rh(COD)Cl]₂, Ag₂CO₃	Dioxane, 80 ℃	55~82	[16]
7	N-Phenyl THIQ	R³=OEt, Ar	[Cu(Sal)₂(NCMe)]₂, TBAC	O₂, CH₃CN, 30 or 60 ℃	50~95	[17]
8	N-Aryl THIQs	R³=OAlkyl	Fe(NO₃)₃•9H₂O	Air, EtOH, 30 ℃	55~93	[18]
9	N-Aryl THIQs	R³=OAlkyl	Co(OAc)₂•4H₂O, NHPI	O₂, CH₃CN, r.t.	66~80	[19]
10	N-Aryl THIQs	R³=OAlkyl, Ph	Co(OAc)₂, NHPI	Air, CH₃CN, 80 ℃	68~100	[20]
11		R³=OAlkyl, Ar	Cu(OTf)₂	p-Benzoquinone, CH₃CN, 70 ℃	53~73	[21]
12	N-Aryl THIQs	R³=OAlkyl, Ph	CoNiFe-LDH	O₂, dioxane, 80 ℃	36~86	[22]

Entry	Amine	P-Nucleophile	Catalyst	Condition	Yield/%	Ref.
1	R¹, R²=H	R³=OAlkyl	FeCl₂	TBHP, MeOH, r.t.~reflux	57~84	[10]
2	N-Aryl THIQs	R³=OAlkyl	MoO₃	O₂, MeOH, 60 ℃	86~95	[12]
3	N-Aryl THIQs or R¹, R²=H	R³=OAlkyl, Ar		Air, CH₃CN, 50 or 60 ℃	37~94	[13]
4	N-Phenyl THIQ	R³=OAlkyl	NaSbCl₆(α-NaphNO₂), NHPI	O₂, CH₃CN, 40 ℃	81~90	[14]
5	N-Aryl THIQs or R¹, R²=H, alkyl	R³=OMe, OEt	AuNPore	O₂ or TBHP, CH₃CN, 80 ℃	52~90	[15]
6	R¹, R²=alkyl	R³=Ph	[Rh(COD)Cl]₂, Ag₂CO₃	Dioxane, 80 ℃	55~82	[16]
7	N-Phenyl THIQ	R³=OEt, Ar	[Cu(Sal)₂(NCMe)]₂, TBAC	O₂, CH₃CN, 30 or 60 ℃	50~95	[17]
8	N-Aryl THIQs	R³=OAlkyl	Fe(NO₃)₃•9H₂O	Air, EtOH, 30 ℃	55~93	[18]
9	N-Aryl THIQs	R³=OAlkyl	Co(OAc)₂•4H₂O, NHPI	O₂, CH₃CN, r.t.	66~80	[19]
10	N-Aryl THIQs	R³=OAlkyl, Ph	Co(OAc)₂, NHPI	Air, CH₃CN, 80 ℃	68~100	[20]
11		R³=OAlkyl, Ar	Cu(OTf)₂	p-Benzoquinone, CH₃CN, 70 ℃	53~73	[21]
12	N-Aryl THIQs	R³=OAlkyl, Ph	CoNiFe-LDH	O₂, dioxane, 80 ℃	36~86	[22]

Entry	Amine	P-Nucleophile	Oxidant	Condition	Yield/%	Ref.
1	N-Aryl THIQs	R³=OAlkyl	DDQ (10 mol%), AIBN (10 mol%), O₂	MeOH, 60 ℃	75~86	[24]
2	N-Aryl THIQs	R³=OAlkyl	I₂ (10 mol%), O₂	MeOH, r.t.	45~75	[25]
3	N-Aryl THIQs	R³=OAlkyl, Ph	TBPA⁺•SbCl₆^- (10 mol%), air	THF, r.t.	73~97	[26]
4	N-Phenyl THIQ	R³=OAlkyl	CBr₄, air	THF, r.t.	80~84	[27]
5	N-Aryl THIQs or R¹=R²=H	R³=OEt	Thiourea (20 mol%), TBHP	CH₃CN, 50 ℃	23~89	[28]
6	N-Aryl THIQs	R³=OAlkyl	Air	DCE, 80 ℃	28~78	[29]
7	N-Aryl THIQs	R³=OAlkyl, Ph	TBHP	CH₃CN, 80 ℃	50~92	[30]

Entry	Amine	P-Nucleophile	Oxidant	Condition	Yield/%	Ref.
1	N-Aryl THIQs	R³=OAlkyl	DDQ (10 mol%), AIBN (10 mol%), O₂	MeOH, 60 ℃	75~86	[24]
2	N-Aryl THIQs	R³=OAlkyl	I₂ (10 mol%), O₂	MeOH, r.t.	45~75	[25]
3	N-Aryl THIQs	R³=OAlkyl, Ph	TBPA⁺•SbCl₆^- (10 mol%), air	THF, r.t.	73~97	[26]
4	N-Phenyl THIQ	R³=OAlkyl	CBr₄, air	THF, r.t.	80~84	[27]
5	N-Aryl THIQs or R¹=R²=H	R³=OEt	Thiourea (20 mol%), TBHP	CH₃CN, 50 ℃	23~89	[28]
6	N-Aryl THIQs	R³=OAlkyl	Air	DCE, 80 ℃	28~78	[29]
7	N-Aryl THIQs	R³=OAlkyl, Ph	TBHP	CH₃CN, 80 ℃	50~92	[30]

Entry	Amine	P-Nucleophile	PC, light source	Condition	Yield/%	Ref.
1	N-Aryl THIQs	R³=OAlkyl, OPh	5 W fluorescent bulb	Air, toluene/H₂O, r.t.	39~91	[32]
2	N-Aryl THIQs	R³=OEt	Rose Bengal, green LEDs	Air, CH₃CN/H₂O at 0.05 mL•min^-1, r.t.	49~60	[33]
3	N-Aryl THIQs	R³=OAlkyl, Ar	5 W blue LEDs	Air, CH₃CN, r.t.	82~92	[34]
4	N-Phenyl THIQ	R³=OMe, OEt	PdF₂₀TPP, light (λ>400 nm)	O₂ bubbling, CH₃CN/MeOH	63~84	[35]
5	N-Aryl THIQs	R³=OAlkyl, Ar	PS-Ir, 7.1 W white LEDs	Air, MeOH, r.t.	39~97	[36]
6	N-Aryl THIQs	R³=OAlkyl, OPh	BODIPY, white LEDs	Air, MeOH, r.t.	42~85	[37]
7	N-Phenyl THIQ	R³=OEt	blue LEDs	CBrCl₃, CH₃CN, r.t.	82	[38]
8	N-Aryl THIQs	R³=OAlkyl	COF-JLU5, 30 W blue LEDs	O₂, MeOH, 25 ℃	63~91	[39]
9	N-Aryl THIQs or R¹=H, alkyl; R²=H, Alkyl, Ph	R³=OAlkyl	Ru(bpy)₃(PF₆)₂, 3 W blue LEDs	Co(dmgH)(dmgH₂)Cl₂, PhCOONa, CH₃CN/DCE, r.t.	36~99	[40]
10	N-Aryl THIQs	R³=OEt, OPh	CPOPs, 23 W white LEDs	Air, MeOH, r.t.	80~94	[41]
11	N-Aryl THIQs or R¹, R²=H, alkyl	R³=OAlkyl, OPh	CsPbBr₃, white LEDs	Air, toluene or THF, r.t.	50~96	[42]
12	N-Aryl THIQs	R³=OAlkyl	N-methyl-3(10H)-Acridone, 6 W blue LEDs	Air, MeOH, r.t.	45~86	[43]
13	N-Aryl THIQs or R¹, R²=H, Me	R³=OMe, Ar	, 5 W blue LEDs	NaHCO₃, DMF	68~91	[44]
14	N-Phenyl THIQ	R³=OEt	EY@UiO-66-NH₂, 16 W green LEDs	Air, MeOH, r.t.	80	[45]
15	N-Phenyl THIQ	P(OEt)₃	, 15 W blue LEDs	Air, toluene/H₂O, r.t.	82	[46]
16	N-Aryl THIQs	R³=OAlkyl	MNPs-Eosin Y, 3 W green LEDs	Air, DMSO, r.t.	86~97	[47]

基于仲膦氧化物和亚磷酸酯的C(sp³)—H磷酰化反应研究进展

Recent Advances in C(sp³)—H Phosphorylation Based on Secondary Phosphine Oxides and Phosphite Esters

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Entry	P-Nucleophile	Condition	Yield/%	Ref.
1	P(OEt)₃	TBPA^+• (15 mol%), p-TsOH (10 mol%), O₂, CH₃CN, 60 ℃	17~94	[54]
2	R'=Et	TBPA^+• (10 mol%), O₂, CH₃CN, 60 ℃	21~96	[55]
3	R'=alkyl, Ph	DDQ, THF, 80 ℃	15~99	[56]
4	R'=alkyl	DDQ, toluene, 80 ℃	22~92	[57]
5	R'=alkyl	Co(ClO₄)₂•6H₂O (10 mol%), air, CH₃CN, 80 ℃	40~95	[58]
6	R'=Me, Et, Bn	NaOAc (20 mol%), LiClO₄, CH₃CN, 6.6 V, r.t., graphite felt	33~89	[59]

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基于仲膦氧化物和亚磷酸酯的C(sp3)—H磷酰化反应研究进展