铑（II）催化的对映选择性环丙烷化反应：使用三甲基硅基乙基和三氯乙基芳基重氮乙酸酯
Enantioselective Dirhodium(II)-Catalyzed Cyclopropanations with Trimethylsilylethyl and Trichloroethyl Aryldiazoacetates.
作者信息
Negretti Solymar, Cohen Carolyn M, Chang Jane J, Guptill David M, Davies Huw M L
机构信息
Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.
出版信息
Tetrahedron. 2015 Sep 30;71(39):7415-7420. doi: 10.1016/j.tet.2015.05.045. Epub 2015 Jun 2.
Abstract
Highly functionalized cyclopropanecarboxylates were readily prepared by rhodium-catalyzed cyclopropanation of alkenes with aryldiazoacetates and styryldiazoaceates, in which the ester functionality is either trimethylsilylethyl (TMSE) or trichlorethyl (TCE). By having labile protecting groups on the ester, chiral triarylcyclopropane carboxylate ligands were conveniently prepared. The asymmetric induction during cyclopropanation is dependent on the nature of the ester group and the chiral dirhodium tetracarboxylate catalyst. The prolinate catalyst Rh(-DOSP) was the optimum catalyst for asymmetric intermolecular cyclopropanation of TMSE diazoesters with styrene, while Rh(-BPCP) was the optimum catalyst for TCE diazoesters.
摘要
通过铑催化烯烃与芳基重氮乙酸酯和苯乙烯基重氮乙酸酯的环丙烷化反应，可轻松制备高度官能化的环丙烷羧酸酯，其中酯官能团为三甲基硅乙基（TMSE）或三氯乙基（TCE）。通过在酯上具有不稳定的保护基团，可方便地制备手性三芳基环丙烷羧酸酯配体。环丙烷化过程中的不对称诱导作用取决于酯基的性质和手性四羧基二铑催化剂。脯氨酸催化剂Rh(-DOSP)是TMSE重氮酯与苯乙烯进行不对称分子内环丙烷化反应的最佳催化剂，而Rh(-BPCP)是TCE重氮酯的最佳催化剂。
相似文献
1
Enantioselective Dirhodium(II)-Catalyzed Cyclopropanations with Trimethylsilylethyl and Trichloroethyl Aryldiazoacetates.
Tetrahedron. 2015 Sep 30;71(39):7415-7420. doi: 10.1016/j.tet.2015.05.045. Epub 2015 Jun 2.
2
Guide to Enantioselective Dirhodium(II)-Catalyzed Cyclopropanation with Aryldiazoacetates.
Tetrahedron. 2013 Jul 8;69(27-28). doi: 10.1016/j.tet.2013.04.075.
3
Diruthenium Tetracarboxylate-Catalyzed Enantioselective Cyclopropanation with Aryldiazoacetates.
Organometallics. 2023 Jun 30;42(15):2122-2133. doi: 10.1021/acs.organomet.3c00268. eCollection 2023 Aug 14.
4
Isotope effects and the nature of selectivity in rhodium-catalyzed cyclopropanations.
J Am Chem Soc. 2003 Dec 24;125(51):15902-11. doi: 10.1021/ja036025q.
5
2,2,2-Trichloroethyl aryldiazoacetates as robust reagents for the enantioselective C-H functionalization of methyl ethers.
J Am Chem Soc. 2014 Dec 24;136(51):17718-21. doi: 10.1021/ja5107404. Epub 2014 Dec 15.
6
Rh2 (S-1,2-NTTL)4 : A novel Rh2 (S-PTTL)4 analog with lower ligand symmetry for asymmetric synthesis of chiral cyclopropylphosphonates.
Chirality. 2014 Nov;26(11):764-74. doi: 10.1002/chir.22349. Epub 2014 Jul 10.
7
Asymmetric intermolecular C-H functionalization of benzyl silyl ethers mediated by chiral auxiliary-based aryldiazoacetates and chiral dirhodium catalysts.
J Org Chem. 2005 Dec 23;70(26):10737-42. doi: 10.1021/jo051747g.
8
Studies of asymmetric styrene cyclopropanation with a rhodium(II) metallopeptide catalyst developed with a high-throughput screen.
Chirality. 2013 Sep;25(9):493-7. doi: 10.1002/chir.22144. Epub 2013 Jun 8.
9
Silica-immobilized chiral dirhodium(II) catalyst for enantioselective carbenoid reactions.
Org Lett. 2013 Dec 20;15(24):6136-9. doi: 10.1021/ol403006r. Epub 2013 Nov 19.
10
Asymmetric Cyclopropanation with 4-Aryloxy-1-sulfonyl-1,2,3-triazoles: Expanding the Range of Rhodium-Stabilized Donor/Acceptor Carbenes to Systems with an Oxygen Donor Group.
J Org Chem. 2022 Nov 4;87(21):13517-13528. doi: 10.1021/acs.joc.2c00978. Epub 2022 Oct 20.
引用本文的文献
1
Rhodium-Stabilized Diarylcarbenes Behaving as Donor/Acceptor Carbenes.
ACS Catal. 2020 Jun 5;10(11):6240-6247. doi: 10.1021/acscatal.0c01131. Epub 2020 Apr 27.
2
[3+3]-Annulation of Cyclic Nitronates with Vinyl Diazoacetates: Diastereoselective Synthesis of Partially Saturated [1,2]Oxazino[2,3-][1,2]oxazines and Their Base-Promoted Ring Contraction to Pyrrolo[1,2-][1,2]oxazine Derivatives.
Molecules. 2023 Mar 28;28(7):3025. doi: 10.3390/molecules28073025.
3
Cannabidiol as Self-Assembly Inducer for Anticancer Drug-Based Nanoparticles.
Molecules. 2022 Dec 23;28(1):112. doi: 10.3390/molecules28010112.
4
Catalytic Enantioselective Sulfur Alkylation of Sulfenamides for the Asymmetric Synthesis of Sulfoximines.
J Am Chem Soc. 2022 Oct 5;144(39):17808-17814. doi: 10.1021/jacs.2c09158. Epub 2022 Sep 26.
5
Asymmetric synthesis of pharmaceutically relevant 1-aryl-2-heteroaryl- and 1,2-diheteroarylcyclopropane-1-carboxylates.
Chem Sci. 2021 Jul 27;12(33):11181-11190. doi: 10.1039/d1sc02474d. eCollection 2021 Aug 25.
6
Rh(III)-Catalyzed Cyclopropanation of Unactivated Olefins Initiated by C-H Activation.
Synlett. 2019 Sep;30(15):1787-1790. doi: 10.1055/s-0039-1690130. Epub 2019 Jul 22.
7
Rh(III)-Catalyzed C-H Activation-Initiated Directed Cyclopropanation of Allylic Alcohols.
J Am Chem Soc. 2019 May 1;141(17):6807-6811. doi: 10.1021/jacs.9b02156. Epub 2019 Apr 18.
本文引用的文献
1
2,2,2-Trichloroethyl aryldiazoacetates as robust reagents for the enantioselective C-H functionalization of methyl ethers.
J Am Chem Soc. 2014 Dec 24;136(51):17718-21. doi: 10.1021/ja5107404. Epub 2014 Dec 15.
2
Role of sterically demanding chiral dirhodium catalysts in site-selective C-H functionalization of activated primary C-H bonds.
J Am Chem Soc. 2014 Jul 9;136(27):9792-6. doi: 10.1021/ja504797x. Epub 2014 Jun 30.
3
Role of ortho-substituents on rhodium-catalyzed asymmetric synthesis of β-lactones by intramolecular C-H insertions of aryldiazoacetates.
Org Lett. 2014 Jun 6;16(11):3036-9. doi: 10.1021/ol5011505. Epub 2014 May 20.
4
Rhodium(II)-catalyzed stereoselective synthesis of allylsilanes.
Org Lett. 2013 Dec 20;15(24):6120-3. doi: 10.1021/ol4028978. Epub 2013 Nov 27.
5
Guide to Enantioselective Dirhodium(II)-Catalyzed Cyclopropanation with Aryldiazoacetates.
Tetrahedron. 2013 Jul 8;69(27-28). doi: 10.1016/j.tet.2013.04.075.
6
Rhodium-catalyzed enantioselective cyclopropanation of electron deficient alkenes.
Chem Sci. 2013 Jul;4(7):2844-2850. doi: 10.1039/C3SC50425E.
7
Rh2(R-TPCP)4-catalyzed enantioselective [3+2]-cycloaddition between nitrones and vinyldiazoacetates.
J Am Chem Soc. 2013 Oct 2;135(39):14516-9. doi: 10.1021/ja4069003. Epub 2013 Sep 20.
8
Enantioselective synthesis of 2-arylbicyclo[1.1.0]butane carboxylates.
Org Lett. 2013 Jan 18;15(2):310-3. doi: 10.1021/ol303217s. Epub 2013 Jan 3.
9
Recent advances in the total synthesis of cyclopropane-containing natural products.
Chem Soc Rev. 2012 Jul 7;41(13):4631-42. doi: 10.1039/c2cs35067j. Epub 2012 May 16.
10
D2-symmetric dirhodium catalyst derived from a 1,2,2-triarylcyclopropanecarboxylate ligand: design, synthesis and application.
J Am Chem Soc. 2011 Nov 30;133(47):19198-204. doi: 10.1021/ja2074104. Epub 2011 Nov 2.
Zotero 插件