In recent years, fluorous chemistry has emerged as one of the promising fields of green chemistry. The term “fluorous” is a coined word meaning having affinity with fluorocarbons. Highly fluorinated compounds, in another words fluorous compounds, are insoluble in general organic solvents or water. However they are highly soluble with fluorous solvents such as perfluoroalkane. Fluorous chemistry is the technique of making use of this property, and it is applied to many organic reactions. Although fluorous solvents are generally immiscible with common organic solvents and water, certain fluorous solvents are able to form homogeneous solutions with some organic solvents at elevated temperatures. The characteristic features of these fluorous solvents is that they have boiling points properties that are almost equal to those of the corresponding hydrocarbons, regardless of their molecular weight, and these solvents have a high solubility of many gases and incombustible property. Taking the advantage of these properties, Horváth et al. accomplished the hydroformylation of olefins using a fluorous rhodium catalyst in perfluoromethylcyclohexane and toluene in 1994.¹⁾ This was regarded as the origin of the fluorous chemistry. This reaction uses perfluoromethylcyclohexane and toluene as solvents, which exist as a biphasic system at room temperature. In this system the fluorous catalyst exists in the fluorous phase and the olefins in the organic phase. However, the two phases form a homogeneous solution when heated. The reaction then proceeds by introduction of carbon monoxide and hydrogen gases. When the reaction is complete and the system is cooled, the two phases reappears, where the resulting product is found in the organic phase and the fluorous catalyst is in the fluorous phase; thus, the catalyst and the product are easily separated. The biphasic system using a fluorous solvent and an organic solvent is called Fluorous Biphase System (FBS), and the multiple phase system is called Fluorous Multiphase System (FMS). The advantages of FBS and FMS are that the resulting product and the catalyst can be easily separated simply by separating the fluorous phase from the other phase after the reaction. After separation, the fluorous phase containing the fluorous catalyst can be reused.

Curran et al. have introduced the use of fluorous substituents (fluorous tags) into non-fluorous substrates for the synthesis of isoxazoline.²⁾ After the reaction, the fluorous product was separated by fractional extraction with dichloromethane, water, and perfluorohexane. Following this report, numerous applications of fluorous chemistry have been made in combinatorial chemistry³⁾ and oligosaccharide syntheses⁴⁾.

Fluorous Solvents

Fluorous Compounds

Fluorous Solvents

D2669	E0485	P0074
H0946	P1420	P0851
H0085	P0837	O0268
O0292	P0856	P1348
P1051	P0839	P0846
T1012

Fluorous Compounds

Fluorous Alkanes, Fluorous Alkenes

H0846	N0601	P1102
T2496	U0076

Fluorous Alcohols

D1101	D2891	E0239
H0845	H1232	H0548
H1233	H1035	H1279
H0649	H0746	N0814
N0600	N0810	O0294
O0114	P0904	P0845
T1701	T2528

Fluorous Carboxylic Acids, Anhydrides and Halides

P1449	B1698	D2465
H0843	H0024	H0337
H0508	H0892	H0658
H0743	N0607	N0605
N0809	O0260	P0764
T2492	T1545	U0067
U0075

Fluorous Esters

H0744	D3589	D3590
H1038	H0594	N0689
M1915	H1033	M2022
M1916	M1912	P1453
M1917	M1914	M1913

Fluorohalides

D3572	D3587	D3573
D2804	D2333	H0844
H1084	H0946	P1084
H0689	H0596	N0808
N0499	P1155	D2329
P1753	T2482	T2479
T1098	T2074	U0081

Fluorous Sulfonic Acids & their derivatives

H1176	H1281	H1055
N0710	N0709	P1098
H0729	N0711	N0677

Other Fluorous Compounds

B2340	E0462	P1363
A1330	H0926	H0467
H1056	H1057	N0645
P1452	U0071	N0872
O0318	M1433	P1754
P1106	P1080	P1081
N0712	H1058	P1162
P1163	T2037	T1770
T2720	T0859	P1134
T0828	U0083