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Synthesis of Alkenyl Ylide Complexes from Reactions of ReOCl2(OEt)(PPh3)2 with Alkynols

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journal contribution
posted on 22.10.2012, 00:00 by Ka Chun Poon, Chuan Shi, Herman H.-Y. Sung, Ian D. Williams, Zhenyang Lin, Guochen Jia
Reactions of both terminal and internal alkynols with ReOCl2(OEt)­(PPh3)2 (1) are described. Treatment of ReOCl2(OEt)­(PPh3)2 (1) with HCCC6H4-2-CH2OH and HCCCH2CH2CH2OH produced the six-membered ylide complexes ReOCl2(C­(CH­(PPh3))-C6H4-CH2O)­(PPh3) (2) and ReOCl2(C­(CH­(PPh3))­CH2CH2CH2O)­(PPh3) (3), respectvely, derived from addition of PPh3 to the terminal alkyne carbon. Similarly, phosphine addition to the terminal alkyne carbon occurred in the reactions of ReOCl2(OEt)­(PPh3)2 (1) with HCCCH2CH­(OH)­Me and HCCCH2CH­(OH)­CH­(OH)­CH2CCH to give the five-membered ylide complexes ReOCl2(C­(CH­(PPh3))­CH2CH2CHMeO)­(PPh3) (5) and {ReOCl2(C­(CH­(PPh3)­CH2CHO)­(PPh3)}2 (6), respectively. Interestingly, related reactions of ReOCl2(OEt)­(PPh3)2 with RCCCH2CH2OH (R = Me, Et, Ph) produced the six-membered ylide complexes ReOCl2(CRC­(PPh3)­CH2CH2O)­(PPh3) (7, R = Me; 8, R = Et; 9, R = Ph), derived from addition of PPh3 to the alkyne carbon closer to the OH group.