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Synthetic studies on and mechanistic insight into [W(CO)5(L)]-catalyzed stereoselective construction of functionalized bicyclo[5.3.0]decane frameworks.
Chemistry. 2010 Sep 17; 16(35):10785-96.C

Abstract

Stereoselective preparation of a variety of synthetically useful functionalized bicyclo[5.3.0]decane derivatives was achieved by tandem cyclization of 3-siloxy-1,3,9-triene-7-yne derivatives based on the electrophilic activation of alkynes catalyzed by [W(CO)(5)(L)]. The reaction proceeded smoothly under photoirradiation, and various substrates were cyclized to give the corresponding bicyclic compounds with up to four chiral centers stereospecifically. Reactions of siloxydienes with a silyl substituent as an equivalent of a hydroxyl group also proceeded with wide generality to afford silyl-substituted bicyclo[5.3.0]decanes, which were highly useful as synthetic intermediates. Stereochemical studies concerning the silyl enol ether moiety suggested that two types of reaction pathway for the formation of seven-membered rings were present. The reaction of (Z)-enol silyl ethers proceeded through Cope rearrangement of cis-divinylcyclopropane intermediates, and that of (E)-enol silyl ethers by 1,4-addition of the dienyl tungsten species at the position δ to the metal atom. In the reactions of siloxydiene derivatives with silyl substituents, all possible diastereomers could be synthesized stereoselectively by changing the geometry of the silyl enol ether and enyne moieties.

Authors+Show Affiliations

Department of Chemistry, Tokyo Institute of Technology, 2-12-1-E1-2 O-okayama, Meguro-ku, Tokyo 152-8551, Japan.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

20680944

Citation

Onizawa, Yuji, et al. "Synthetic Studies On and Mechanistic Insight Into [W(CO)5(L)]-catalyzed Stereoselective Construction of Functionalized Bicyclo[5.3.0]decane Frameworks." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 16, no. 35, 2010, pp. 10785-96.
Onizawa Y, Hara M, Hashimoto T, et al. Synthetic studies on and mechanistic insight into [W(CO)5(L)]-catalyzed stereoselective construction of functionalized bicyclo[5.3.0]decane frameworks. Chemistry. 2010;16(35):10785-96.
Onizawa, Y., Hara, M., Hashimoto, T., Kusama, H., & Iwasawa, N. (2010). Synthetic studies on and mechanistic insight into [W(CO)5(L)]-catalyzed stereoselective construction of functionalized bicyclo[5.3.0]decane frameworks. Chemistry (Weinheim an Der Bergstrasse, Germany), 16(35), 10785-96. https://doi.org/10.1002/chem.201001003
Onizawa Y, et al. Synthetic Studies On and Mechanistic Insight Into [W(CO)5(L)]-catalyzed Stereoselective Construction of Functionalized Bicyclo[5.3.0]decane Frameworks. Chemistry. 2010 Sep 17;16(35):10785-96. PubMed PMID: 20680944.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Synthetic studies on and mechanistic insight into [W(CO)5(L)]-catalyzed stereoselective construction of functionalized bicyclo[5.3.0]decane frameworks. AU - Onizawa,Yuji, AU - Hara,Masahiro, AU - Hashimoto,Takuya, AU - Kusama,Hiroyuki, AU - Iwasawa,Nobuharu, PY - 2010/8/4/entrez PY - 2010/8/4/pubmed PY - 2011/1/19/medline SP - 10785 EP - 96 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 16 IS - 35 N2 - Stereoselective preparation of a variety of synthetically useful functionalized bicyclo[5.3.0]decane derivatives was achieved by tandem cyclization of 3-siloxy-1,3,9-triene-7-yne derivatives based on the electrophilic activation of alkynes catalyzed by [W(CO)(5)(L)]. The reaction proceeded smoothly under photoirradiation, and various substrates were cyclized to give the corresponding bicyclic compounds with up to four chiral centers stereospecifically. Reactions of siloxydienes with a silyl substituent as an equivalent of a hydroxyl group also proceeded with wide generality to afford silyl-substituted bicyclo[5.3.0]decanes, which were highly useful as synthetic intermediates. Stereochemical studies concerning the silyl enol ether moiety suggested that two types of reaction pathway for the formation of seven-membered rings were present. The reaction of (Z)-enol silyl ethers proceeded through Cope rearrangement of cis-divinylcyclopropane intermediates, and that of (E)-enol silyl ethers by 1,4-addition of the dienyl tungsten species at the position δ to the metal atom. In the reactions of siloxydiene derivatives with silyl substituents, all possible diastereomers could be synthesized stereoselectively by changing the geometry of the silyl enol ether and enyne moieties. SN - 1521-3765 UR - https://www.unboundmedicine.com/medline/citation/20680944/Synthetic_studies_on_and_mechanistic_insight_into_[W_CO_5_L_]_catalyzed_stereoselective_construction_of_functionalized_bicyclo[5_3_0]decane_frameworks_ L2 - https://doi.org/10.1002/chem.201001003 DB - PRIME DP - Unbound Medicine ER -