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. 2017 Oct 11;117(19):12564-12580.
doi: 10.1021/acs.chemrev.7b00385. Epub 2017 Sep 14.

Acyclic Quaternary Carbon Stereocenters via Enantioselective Transition Metal Catalysis

Jiajie Feng  1 , Michael Holmes  1 , Michael J Krische  1
Affiliations

Acyclic Quaternary Carbon Stereocenters via Enantioselective Transition Metal Catalysis

Jiajie Feng et al. Chem Rev. .

Abstract

Whereas numerous asymmetric methods for formation of quaternary carbon stereocenters in cyclic systems have been documented, the construction of acyclic quaternary carbon stereocenters with control of absolute stereochemistry remains a formidable challenge. This Review summarizes enantioselective methods for the construction of acyclic quaternary carbon stereocenters from achiral or chiral racemic reactants via transition metal catalysis.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Commercial pharmaceutical and agrochemical products bearing cyclic and, less frequently encountered, acyclic quaternary carbon stereocenters.
Scheme 1
Scheme 1
Early examples of the enantioselective formation of quaternary carbon stereocenters involve cyclic systems.
Scheme 2
Scheme 2
Enantioselective copper-catalyzed allylic substitution to form acyclic quaternary carbon stereocenters.
Scheme 3
Scheme 3
Enantioselective copper-catalyzed allylic substitution of organomagnesium, organolithium and organoboron reagents to form acyclic quaternary carbon stereocenters.
Scheme 4
Scheme 4
Copper-free enantioselective allylic substitutions to form acyclic quaternary carbon stereocenters.
Scheme 5
Scheme 5
Use of vinyl- and arylmetal reagents in enantioselective copper-catalyzed SN2′ reactions to form acyclic quaternary carbon stereocenters.
Scheme 6
Scheme 6
Enantioselective alkynylation, allenylation and formylation of allylic phosphates to form acyclic quaternary carbon stereocenters.
Scheme 7
Scheme 7
Enantioselective formation of acyclic quaternary carbon stereocenters via palladium-catalyzed allyl-allyl cross-coupling.
Scheme 8
Scheme 8
Enantioselective copper-catalyzed conjugate addition of organozinc reagents to form acyclic quaternary carbon stereocenters.
Scheme 9
Scheme 9
Enantioselective copper-catalyzed conjugate addition of organoaluminum, organozirconium and organoboron reagents to form acyclic quaternary carbon stereocenters.
Scheme 10
Scheme 10
Enantioselective rhodium-catalyzed conjugate addition of organoboron reagents to form acyclic quaternary carbon stereocenters.
Scheme 11
Scheme 11
Enantioselective iridium catalyzed carbonyl allylation to form acyclic quaternary carbon stereocenters.
Scheme 12
Scheme 12
Enantioselective NHK-coupling of allyl chlorides and aldehydes to form acyclic quaternary carbon stereocenters.
Scheme 13
Scheme 13
Enantioselective nickel catalyzed hydrovinylation of α-substituted styrenes to form acyclic quaternary carbon stereocenters.
Scheme 14
Scheme 14
Enantioselective (oxidative) Heck reaction of arylboronic acids, indoles and vinyl triflates with trisubstituted olefinic alcohols to form remote acyclic quaternary carbon stereocenters.
Scheme 15
Scheme 15
Enantioselective palladium-catalyzed Tsuji-Trost reactions to form acyclic quaternary carbon stereocenters.
Scheme 16
Scheme 16
Enantioselective iridium- and rhodium-catalyzed Tsuji-Trost reactions for stereodivergent formation of acyclic quaternary carbon stereocenters.
Scheme 17
Scheme 17
Enantioselective iridium-catalyzed Tsuji-Trost reactions to form acyclic quaternary carbon stereocenters.
Scheme 18
Scheme 18
Enantioselective rhodium-catalyzed Tsuji-Trost reactions to form acyclic quaternary carbon stereocenters.
Scheme 19
Scheme 19
Miscellaneous enantioselective transformations of stabilized π-nucleophiles to form acyclic quaternary carbon stereocenters.
Scheme 20
Scheme 20
Enantioselective three component coupling of indoles, α-diazo esters and imines to form acyclic quaternary carbon stereocenters.
Scheme 21
Scheme 21
Desymmetrization via enantioselective cleavage of strained rings to form acyclic quaternary carbon stereocenters.
Scheme 22
Scheme 22
Desymmetrization via enantioselective ring opening metathesis of 3,3-disubstituted cyclopropenes to form acyclic quaternary carbon stereocenters.
Scheme 23
Scheme 23
Desymmetrization via enantioselective palladium-catalyzed C-H functionalization to form acyclic quaternary carbon stereocenters.
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