Chlorotrimethylsilane → 2-(Bis(3,5-di(tert-butyl)-4-methoxyphenyl)phosphino)phenylphosphine

HRID 1581622Notes

Reaction equation

HRID 1581622 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]([P:17]([C:31]2[CH:36]=[C:35]([C:37]([CH3:40])([CH3:39])[CH3:38])[C:34]([O:41][CH3:42])=[C:33]([C:43]([CH3:46])([CH3:45])[CH3:44])[CH:32]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=2[P:24](OCC)OCC)[CH:8]=[C:9]([C:13]([CH3:16])([CH3:15])[CH3:14])[C:10]=1[O:11][CH3:12])([CH3:4])([CH3:3])[CH3:2].[H-].[Al+3].[Li+].[H-].[H-].[H-].C[Si](Cl)(C)C>>[C:13]([C:9]1[CH:8]=[C:7]([P:17]([C:31]2[CH:36]=[C:35]([C:37]([CH3:40])([CH3:39])[CH3:38])[C:34]([O:41][CH3:42])=[C:33]([C:43]([CH3:46])([CH3:45])[CH3:44])[CH:32]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=2[PH2:24])[CH:6]=[C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[C:10]=1[O:11][CH3:12])([CH3:14])([CH3:15])[CH3:16]

Participants

4

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 12115811Diethyl 2-[bis(3,5-di-t-butyl-4-methoxyphenyl)phosphino]phenylphosphoniteHCID 21226445Aluminium lithium hydride

Product 1

HCID 113766522-(Bis(3,5-di(tert-butyl)-4-methoxyphenyl)phosphino)phenylphosphine

Procedure

For example, referring to the reaction sequence shown below, 2-bromophenol (4) is reacted with trifluoromethanesulfonic anhydride to form 2-(trifluoromethanesulfonyl)oxy-bromobenzene (5), which is then reacted with bis(3,5-di-t-butyl-4-methoxyphenyl)phosphine oxide in the presence of a palladium complex catalyst to obtain bis(3,5-di-t-butyl-4-methoxyphenyl)(2-bromophenyl)phosphine oxide (6). Next, the compound (6) is reduced with trichlorosilane in the presence of N,N′-dimethylaniline to obtain bis(3,5-di-t-butyl-4-methoxyphenyl)(2-bromophenyl)phosphine (7). The compound (7) is reacted with diethyl chlorophosphonite in the presence of n-butyllithium to obtain diethyl 2-[bis(3,5-di-t-butyl-4-methoxyphenyl)phosphino]phenylphosphonite (8). Then, the compound (8) is reduced with lithium aluminum hydride in the presence of trimethylsilyl chloride to form 2-[bis(3,5-di-t-butyl-4-methoxyphenyl)phosphino]phenylphosphine (9). Thereafter, in the presence of n-butyllithium, the compound (9) is reacted with dimesylate of (2R,5R)-2,5-hexanediol, which is producible, for example, according to the method described in the literature (Tetrahedron: Asymmetry, 1991, 2, 569), whereby the aimed (S,S)-Me-UCAP-DTBM (3) can be produced in a high efficiency.

Sources & evidence

ORD record
ord-103a353f76d94c2ca70154936db84e33
Source dataset
uspto-grants-2004_05
Patent number
US06730629B2

Reaction notes

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