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Stereoselective Rh2(S-IBAZ)4-catalyzed cyclopropanation of alkenes, alkynes, and allenes: asymmetric synthesis of diacceptor cyclopropylphosphonates and alkylidenecyclopropanes.
J Am Chem Soc. 2013 Jan 30; 135(4):1463-70.JA

Abstract

A mild and highly stereoselective rhodium(II)-catalyzed cyclopropanation of alkenes, alkynes, and allenes with diacceptor diazo compounds is reported. Using the phosphonate moiety as an efficient trans-directing group, the first catalytic asymmetric route to diacceptor cycloprop(en)ylphosphonates was developed by employing an α-cyano diazophosphonate and Rh(2)(S-IBAZ)(4) as chiral catalyst. The isosteric character of phosphonic and carboxylic acid derivatives allowed the alternative use of an α-cyano diazo ester in the process, leading to α-cyano cycloprop(en)ylcarboxylates in high yields and stereoselectivities. Taking advantage of the particular reactivity of the cyanocarbene intermediates involved in this system, the scope of compatible substrates could be extended to substituted allenes, leading to the development of the first catalytic enantioselective method for the synthesis of diacceptor alkylidenecyclopropanes.

Authors+Show Affiliations

Centre in Green Chemistry and Catalysis, Department of Chemistry, Université de Montréal, P.O. Box 6128, Station Downtown, Montréal, Québec, Canada H3C 3J7.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

23289770

Citation

Lindsay, Vincent N G., et al. "Stereoselective Rh2(S-IBAZ)4-catalyzed Cyclopropanation of Alkenes, Alkynes, and Allenes: Asymmetric Synthesis of Diacceptor Cyclopropylphosphonates and Alkylidenecyclopropanes." Journal of the American Chemical Society, vol. 135, no. 4, 2013, pp. 1463-70.
Lindsay VN, Fiset D, Gritsch PJ, et al. Stereoselective Rh2(S-IBAZ)4-catalyzed cyclopropanation of alkenes, alkynes, and allenes: asymmetric synthesis of diacceptor cyclopropylphosphonates and alkylidenecyclopropanes. J Am Chem Soc. 2013;135(4):1463-70.
Lindsay, V. N., Fiset, D., Gritsch, P. J., Azzi, S., & Charette, A. B. (2013). Stereoselective Rh2(S-IBAZ)4-catalyzed cyclopropanation of alkenes, alkynes, and allenes: asymmetric synthesis of diacceptor cyclopropylphosphonates and alkylidenecyclopropanes. Journal of the American Chemical Society, 135(4), 1463-70. https://doi.org/10.1021/ja3099728
Lindsay VN, et al. Stereoselective Rh2(S-IBAZ)4-catalyzed Cyclopropanation of Alkenes, Alkynes, and Allenes: Asymmetric Synthesis of Diacceptor Cyclopropylphosphonates and Alkylidenecyclopropanes. J Am Chem Soc. 2013 Jan 30;135(4):1463-70. PubMed PMID: 23289770.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Stereoselective Rh2(S-IBAZ)4-catalyzed cyclopropanation of alkenes, alkynes, and allenes: asymmetric synthesis of diacceptor cyclopropylphosphonates and alkylidenecyclopropanes. AU - Lindsay,Vincent N G, AU - Fiset,Dominic, AU - Gritsch,Philipp J, AU - Azzi,Soula, AU - Charette,André B, Y1 - 2013/01/15/ PY - 2013/1/8/entrez PY - 2013/1/8/pubmed PY - 2013/7/24/medline SP - 1463 EP - 70 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 135 IS - 4 N2 - A mild and highly stereoselective rhodium(II)-catalyzed cyclopropanation of alkenes, alkynes, and allenes with diacceptor diazo compounds is reported. Using the phosphonate moiety as an efficient trans-directing group, the first catalytic asymmetric route to diacceptor cycloprop(en)ylphosphonates was developed by employing an α-cyano diazophosphonate and Rh(2)(S-IBAZ)(4) as chiral catalyst. The isosteric character of phosphonic and carboxylic acid derivatives allowed the alternative use of an α-cyano diazo ester in the process, leading to α-cyano cycloprop(en)ylcarboxylates in high yields and stereoselectivities. Taking advantage of the particular reactivity of the cyanocarbene intermediates involved in this system, the scope of compatible substrates could be extended to substituted allenes, leading to the development of the first catalytic enantioselective method for the synthesis of diacceptor alkylidenecyclopropanes. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/23289770/Stereoselective_Rh2_S_IBAZ_4_catalyzed_cyclopropanation_of_alkenes_alkynes_and_allenes:_asymmetric_synthesis_of_diacceptor_cyclopropylphosphonates_and_alkylidenecyclopropanes_ L2 - https://doi.org/10.1021/ja3099728 DB - PRIME DP - Unbound Medicine ER -