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Review
. 2016 Feb 18;55(8):2636-49.
doi: 10.1002/anie.201507151. Epub 2016 Jan 13.

Catalytic Enantioselective Functionalization of Unactivated Terminal Alkenes

John R Coombs  1 , James P Morken  2
Affiliations
Review

Catalytic Enantioselective Functionalization of Unactivated Terminal Alkenes

John R Coombs et al. Angew Chem Int Ed Engl. .

Abstract

Terminal alkenes are readily available functional groups which appear in α-olefins produced by the chemical industry, and they appear in the products of many contemporary synthetic reactions. While the organic transformations that apply to alkenes are amongst the most studied reactions in all of chemical synthesis, the number of reactions that apply to nonactivated terminal alkenes in a catalytic enantioselective fashion is small in number. This Minireview highlights the cases where stereocontrol in catalytic reactions of 1-alkenes is high enough to be useful for asymmetric synthesis.

Keywords: alkenes; asymmetric synthesis; chirality; enantioselective catalysis; transition metals.

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Figures

Figure 1
Figure 1
X-ray structure of [PdCl2{(R)-MeO-MOP}2]
Figure 2
Figure 2
Favored catalyst conformation and quadrant diagrams showing preferred olefin binding modes.
Figure 3
Figure 3
Proposed stereochemical model for olefin coordination in asymmetric C-H addition of pyridines to 1-alkenes.
Figure 4
Figure 4
Stereochemical model for the Ir-salen catalyzed cyclopropanation of terminal alkenes.
Figure 5
Figure 5
Proposed stereochemical model for the Zr-catalyzed methylalumination of 1-alkenes.
Scheme 1
Scheme 1
Quadrant diagrams describe pathways for migratory insertion of a prochiral substituted alkene into the M-A bond in a representative chiral transition metal complex. The shaded quadrant indicates and area of steric encumbrance established by the ligand framework.
Scheme 2
Scheme 2
Mechanisms for transition-metal-catalyzed hydrosilylation.
Scheme 3
Scheme 3
Catalytic hydrosilylation of terminal alkenes developed by Hayashi.
Scheme 4
Scheme 4
A. Comparison of substituted MOP ligands with varying substitution at the 2'-napthyl position. B. Crystal structure of [PdCl2(R-MeO-MOP)2].
Scheme 5
Scheme 5
Catalytic cycle for Rh-catalyzed olefin hydroformylation.
Scheme 6
Scheme 6
Rh-Catalyzed hydroformylation of alkenes developed by Takaya.
Scheme 7
Scheme 7
Branched-selective Rh-catalyzed hydroformylation of alkenes reported by Clarke and Cobey.
Scheme 8
Scheme 8
Widenhoefer's gold(I) catalyzed hydroamination of alkenes wth cyclic ureas.
Scheme 9
Scheme 9
Zr-Catalyzed C-H addition of 2-picoline to 1-octene reported by Rodewald and Jordan.
Scheme 10
Scheme 10
Hou's asymmetric C-H bond addition of pyridines to 1-alkenes.
Scheme 11
Scheme 11
Early examples of a highly enantioselective dihydroxylation of terminal alkenes reported by Hirama.
Scheme 12
Scheme 12
Sharpless' asymmetric dihydroxylation applied to 1-alkenes.
Scheme 13
Scheme 13
Pt-Catalyzed asymmetric epoxidation of alkenes developed by Strukul.
Scheme 14
Scheme 14
Katsuki's Ti(salen)-catalyzed asymmetric epoxidation of terminal alkenes.
Scheme 15
Scheme 15
Berkessel's Ti(salen)-catalyzed asymmetric epoxidation of terminal alkenes.
Scheme 16
Scheme 16
Pd(binap)-catalyzed chlorohydrin synthesis from 1-alkenes as documented by Henry.
Scheme 17
Scheme 17
X. Peter Zhang's asymmetric aziridination of 1-alkenes with TcesN3.
Scheme 18
Scheme 18
Katsuki's Ru(salalen)-catalyzed aziridination of terminal alkenes.
Scheme 19
Scheme 19
Selected examples of asymmetric transition-metal-catalzed cyclopropanation of 1-hexene.
Scheme 20
Scheme 20
Katsuki's Ir-catalyzed asymmetric cyclopropanation of alkenes.
Scheme 21
Scheme 21
Zhang's Co-catalyzed asymmetric terminal alkene cyclopropanation followed by chemoselective reduction.
Scheme 22
Scheme 22
Negishi's Zr-catalyzed carboalumination (ZACA) of terminal alkenes.
Scheme 23
Scheme 23
Pt-Catalyzed enantioselective diboration of terminal alkenes reported in 2009.
Scheme 24
Scheme 24
Optimized Pt-catalyzed asymemtric alkene diboration.
Scheme 25
Scheme 25
Single-flask asymmetric diboration/cross-coupling (DCC) applied to terminal alkenes.
Scheme 26
Scheme 26
Nishiyama's Rh(Phebox)-catalyzed diboration/oxidation of terminal alkenes.
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References

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