Acid-Induced Reactions of 1,2-Oxaphosphetane Complexes

作者：Kyri Andreas W; Schnakenburg Gregor; Streubel Rainer^*

来源：Organometallics, 2017, 36(18): 3605-3612.

DOI：10.1021/acs.organomet.7b00520

Selective P-O bond activation of 1,2-oxaphosphetane complexes [(OC)(5)W(P{CH(SiMe3)(2)}CH2CRR'O)] (R/R' = H/H (1a), H/CH3 (1b), H/CF3 (1c), CF3/CF3 (1d)) was achieved using different Bronsted acids. In case of acids with nucleophilic anions, such as HCl and HBF4OEt(2), the corresponding halophosphane complexes [(OC)(5)W(XP{CH(SiMe3)(2)}CH2CRR'OH] (X = Cl (2a-c), F (3c,d)) resulted as ring-opened products; 2b could be closed again with (BuLi)-Bu-t/12-crown-4. In contrast, trifluoromethanesulfonic acid could be used to initiate either a ring-opening hydrolysis with a subsequent cleavage of the P-M bond to yield PH(O){CH(SiMe3)(2)}{CH2C(CF3)(2)OH} (7) or, in the presence of nitriles, a ring expansion yielding [(OC)(5)W(P{CH(SiMe3)(2)}CH2CH2OCR = N)] (R = CH3 (5a), Ph (5b), C(CH3)(3) (5c)). P-O bond cleavage in 1a was achieved using the Lewis acidic catechol(chloro)borane to give [(OC)(5)W(P{CH(SiMe3)(2)}CH2CH(CH3)OBcat}Cl)] (8; cat = catechol).

• 出版日期2017-9-25