Synthesis of optically active allenyltitaniums having axial chirality by the reaction of optically active propargylic compounds with a Ti(O-i-Pr)4/2i- PrMgCl reagent

Tetrahedron Letters

Volumn 39, Issue 25, 1998, Pages 4551-4554

  Okamoto, Sentaro ^a   An, Duk Keun ^a   Sato, Fumie ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

Alcohols; Asymmetric synthesis; Elimination; Titanium and compounds

Indexed keywords

ALCOHOL DERIVATIVE; TITANIUM DERIVATIVE;

ARTICLE; CHIRALITY; REACTION ANALYSIS; SYNTHESIS;

EID: 0032543484     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)00829-6     Document Type: Article

References (24)

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2. [1] Kulinkovich OG, Sviridov SV, Vasilevski DA. Synthesis 1991;234. Kasatkin A, Nakagawa T, Okamoto S, Sato F. J. Am. Chem. Soc. 1995;117:3881-3882. Harada K, Urabe H, Sato F. Tetrahedron Lett. 1995;36:3203-3206. Takayanagi Y, Yamashita K, Yoshida Y, Sato F. J. Chem. Soc., Chem. Commun. 1996;1725-1726.
3. [1] Kulinkovich OG, Sviridov SV, Vasilevski DA. Synthesis 1991;234. Kasatkin A, Nakagawa T, Okamoto S, Sato F. J. Am. Chem. Soc. 1995;117:3881-3882. Harada K, Urabe H, Sato F. Tetrahedron Lett. 1995;36:3203-3206. Takayanagi Y, Yamashita K, Yoshida Y, Sato F. J. Chem. Soc., Chem. Commun. 1996;1725-1726.
4. [1] Kulinkovich OG, Sviridov SV, Vasilevski DA. Synthesis 1991;234. Kasatkin A, Nakagawa T, Okamoto S, Sato F. J. Am. Chem. Soc. 1995;117:3881-3882. Harada K, Urabe H, Sato F. Tetrahedron Lett. 1995;36:3203-3206. Takayanagi Y, Yamashita K, Yoshida Y, Sato F. J. Chem. Soc., Chem. Commun. 1996;1725-1726.
5. [2] Nakagawa T, Kasatkin A, Sato F. Tetrahedron Lett. 1995;36:3207-3210.
6. [3] For synthesis of chiral allenyl metals having axial chirality and their synthetic applications; see, Si: Masse CE, Panek JS. Chem. Rev. 1995;95: 1293-1316. Sn: Marshall JA. Chem. Rev. 1996;96:31-47. B: Matsumoto Y, Naito M, Uozumi Y, Hayashi T. J. Chem. Soc. Chem. Commun. 1993;1468-1469.
7. [3] For synthesis of chiral allenyl metals having axial chirality and their synthetic applications; see, Si: Masse CE, Panek JS. Chem. Rev. 1995;95: 1293-1316. Sn: Marshall JA. Chem. Rev. 1996;96:31-47. B: Matsumoto Y, Naito M, Uozumi Y, Hayashi T. J. Chem. Soc. Chem. Commun. 1993;1468-1469.
8. [3] For synthesis of chiral allenyl metals having axial chirality and their synthetic applications; see, Si: Masse CE, Panek JS. Chem. Rev. 1995;95: 1293-1316. Sn: Marshall JA. Chem. Rev. 1996;96:31-47. B: Matsumoto Y, Naito M, Uozumi Y, Hayashi T. J. Chem. Soc. Chem. Commun. 1993;1468-1469.
9. 2
10. 2
11. 6) for (R)-enantiomer with 86% ee (Meyers Al, Knaus G, Kamata K, Ford ME. J. Am. Chem. Soc. 1976;98:567-576). The e.e. value and absolute configuration of 6 shown in entries 3 and 4 were determined by GLC analysis (Chirasil-DEX CB, Chrompack) after derivatization to 4,8-dimethyl-2,3-nonadiene (15). The procedure for conversion of 6 (entry 3) to 15 is shown below. The authentic 15 having a (R)-configuration was prepared from 12 (shown in note 4). (equation presented)
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15. [8] A similar reaction mechanism to that outlined in Scheme 1 has been proposed for the organocopper-induced substitution reaction of propargylic compounds which involves the formation of the π-complex between the copper and the acetylenic moiety of propargylic derivatives and subsequent elimination of the leaving group via a syn or anti pathway. Alexakis A. Pure Appl. Chem. 1992;64:387-392 and references cited therein.
16. [9] March J. :Advanced Organic Chemistry: Reactions, Mechanism, and Structure. Tokyo: McGraw-Hill Kogakusha, 1977;Chapter 9.
17. [10] Syn-elimination reactions of β-oxysubstituted organometallics via the metal-oxygen coordination have been reported. Sugita T, Nishimoto K, Ichikawa K. Chem. Lett. 1973:607-610. Brown HC, Hamaoka T, Ravindran N. J. Am. Chem. Soc. 1973;95:6456-6457. Shimizu N, Sakai M, Tsuno Y. Chem. Lett. 1990;2207-2208. Maeda, K, Shinokubo H, Oshima K. J. Org. Chem. 1996;61:6770-6771 and references cited therein. See also ref. 8.
18. [10] Syn-elimination reactions of β-oxysubstituted organometallics via the metal-oxygen coordination have been reported. Sugita T, Nishimoto K, Ichikawa K. Chem. Lett. 1973:607-610. Brown HC, Hamaoka T, Ravindran N. J. Am. Chem. Soc. 1973;95:6456-6457. Shimizu N, Sakai M, Tsuno Y. Chem. Lett. 1990;2207-2208. Maeda, K, Shinokubo H, Oshima K. J. Org. Chem. 1996;61:6770-6771 and references cited therein. See also ref. 8.
19. [10] Syn-elimination reactions of β-oxysubstituted organometallics via the metal-oxygen coordination have been reported. Sugita T, Nishimoto K, Ichikawa K. Chem. Lett. 1973:607-610. Brown HC, Hamaoka T, Ravindran N. J. Am. Chem. Soc. 1973;95:6456-6457. Shimizu N, Sakai M, Tsuno Y. Chem. Lett. 1990;2207-2208. Maeda, K, Shinokubo H, Oshima K. J. Org. Chem. 1996;61:6770-6771 and references cited therein. See also ref. 8.
20. [10] Syn-elimination reactions of β-oxysubstituted organometallics via the metal-oxygen coordination have been reported. Sugita T, Nishimoto K, Ichikawa K. Chem. Lett. 1973:607-610. Brown HC, Hamaoka T, Ravindran N. J. Am. Chem. Soc. 1973;95:6456-6457. Shimizu N, Sakai M, Tsuno Y. Chem. Lett. 1990;2207-2208. Maeda, K, Shinokubo H, Oshima K. J. Org. Chem. 1996;61:6770-6771 and references cited therein. See also ref. 8.
21. 6
22. [12] Threo/erythro notation conforms to the definition suggested by Noyori and co-workers. Noyori R, Nishida I, Sakata J. J. Am. Chem. Soc. 1981;103:2106-2108.
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