Table 1.

Screening of reaction conditions. (a) One‐pot reaction scheme for electrochemical WOR using [Ph₂RP(OR¹)]⁺ (R=Ph, Me, Et and R¹=Me, Et) in the presence of substoichiometric amounts of Lewis acid (LA), (b) different [Ph₂RP(OR¹)]⁺, (c) alkyl electrophiles RX, (d) carbonyl compounds, and (e) olefins produced by electrochemical WOR.

Entry[a]	WE[b]	LA[c]	[Ph2RP(OR1)]+[d]	Alkyl electrophile[e]	Carbonyl compound[f]	Olefin	Yield
1	Ag	–	[Ph3P(OMe)]+	MeOTf	PhCHO	PhCH=CH2	<10 %
2	Agg	Sc3+	[Ph3P(OMe)]+	MeOTf	PhCHO	PhCH=CH2	63 %
3	GCh	Sc3+	[Ph3P(OMe)]+	MeOTf	PhCHO	PhCH=CH2	41 %
4	Ag	Yb3+i	[Ph3P(OMe)]+	MeOTf	PhCHO	PhCH=CH2	33 %
5	Ag	Sc3+	[Ph2MeP(OMe)]+	MeOTf	PhCHO	PhCH=CH2	31 %
6	Ag	Sc3+	[Ph2EtP(OMe)]+j	MeOTf	PhCHO	PhCH=CH2	–
7	Ag	Sc3+	[Ph3P(OEt)]+	EtOTf	PhCHO	PhCH=CHCH3	67 %
8	Ag	Sc3+	[Ph3P(OMe)]+	PhCH2Br	PhCHO	PhCH=CHPh	43 %
9	Ag	Sc3+	[Ph3P(OMe)]+	MeOTf	CyCHO	CyCH=CH2	57 %
10	Ag	Sc3+	[Ph3P(OMe)]+	MeOTf	FuCHO	FuCH=CH2	46 %
11	Ag	Sc3+	[Ph3P(OMe)]+	MeOTf	Ph2CO	Ph2C=CH2	22 %

[a] Reaction conditions: all the experiments were conducted under N₂ atmosphere (glove box), 0.175 m TBAPF₆ as supporting electrolyte, dried CH₃CN prior to use as solvent (total volume 3 mL), electrolysis in separated (by glass frit) two electrode cell setup at a constant current (chronopotentiometry; CP at 4.5 mA) using a Pt foil as counter electrode (0.5×0.5 cm working area). [b] working electrode (WE) (0.5×0.5 cm working area). [c] highest yield of TPP and WOR was achieved with 0.02 m (0.6 equiv) LA. [d] electrolysis (2 h) was conducted with 0.032 m [Ph₂RP(OR₁)]⁺ in the presence of 0.6 equiv LA and formation of TPP was confirmed analyzing the solution by ³¹P(¹H) NMR. [e] 0.048 m alkyl halide was added to the working compartment after 2 h of electrolysis and stirred for additional 30 minutes to prepare the phosphonium salt in situ. [f] 0.048 m aldehyde and/or ketone added further to the working compartment. [g] Ag foil 0.1 mm thick connected to with copper wire and copper tape (under an identical condition Cu foil, Mg foil and Ni foam did not produce alkene), [h] glassy carbon rod (GC; 6 mm diameter). [i] 0.02 m Yb(OTf)₃; other LA (Fe³⁺, Ni²⁺, Zn²⁺ and B(OPh)₃) remain ineffective for one‐pot WOR. [j] [R₃POMe](OTf) (R=nBu and n‐oct) did not produce any olefin due to poor TPP regeneration (Figures S40 and S41).