Office of Jury Commissioner: For the period July 1, 2013 through June 30, 2015

Copper-catalyzed, directed addition of Grignard reagents across the strained CC bond of cyclopropene-3-carboxamides was developed. It was demonstrated that the amide functionality serves as an ultimate directing group allowing for highly efficient control of diastereoselectivity of addition including stereoselectivity of electrophilic trapping with prochiral aldehydes. Also, regioselectivity of carbomagnesiation of cyclopropenes with a monosubstituted double bond is investigated. It was shown that in many cases this selectivity is controlled by steric factors and allows for preparation of products with a “reversed” regiochemistry

Directed Cu(I)-Catalyzed Carbomagnesiation of 1‑Arylcycloprop-2-ene-1-carboxamides En Route to Densely Substituted Functionalized Cyclopropanes

Copper-catalyzed, directed addition of Grignard reagents across the strained CC bond of cyclopropene-3-carboxamides was developed. It was demonstrated that the amide functionality serves as an ultimate directing group allowing for highly efficient control of diastereoselectivity of addition including stereoselectivity of electrophilic trapping with prochiral aldehydes. Also, regioselectivity of carbomagnesiation of cyclopropenes with a monosubstituted double bond is investigated. It was shown that in many cases this selectivity is controlled by steric factors and allows for preparation of products with a “reversed” regiochemistry

B(C₆F₅)₃-Catalyzed Allylation of Secondary Benzyl Acetates with Allylsilanes

A highly effective protocol for allylation of secondary benzylic alcohol derivatives with allylsilanes in the presence of catalytic amounts of B(C6F5)3 has been developed. Some additional functionalities, such as bromo, acetoxy, and primary benzyloxy groups, were tolerated under these conditions

Rhodium-Catalyzed Hydroformylation of Cyclopropenes

The first catalytic diastereo- and enantioselective hydroformylation of cyclopropenes was demonstrated. The reaction proceeds efficiently under very mild conditions and low catalyst loadings providing high yields of cyclopropylcarboxaldehydes. This novel methodology represents a convenient, atom-economic approach toward optically active cyclopropylcarboxaldehydes from readily available prochiral cyclopropenes

Transition Metal-Catalyzed Hydro-, Sila-, and Stannastannation of Cyclopropenes: Stereo- and Regioselective Approach toward Multisubstituted Cyclopropyl Synthons

The first highly efficient, stereo- and regioselective palladium-catalyzed hydro-, sila-, and stannastannation of cyclopropenes to give multisubstituted cyclopropylstannanes have been developed. It was shown that the addition across the double bond of cyclopropene is generally controlled by steric factors and proceeds from the least hindered face. The directing effect of alkoxymethyl substituents in the hydrostannation reaction of 3,3-disubstituted cyclopropenes was demonstrated. This methodology represents a powerful and atom-economic approach toward a wide variety of highly substituted cyclopropylstannanes, important building blocks unavailable by other methods

B(C₆F₅)₃-Catalyzed Allylation of Propargyl Acetates with Allylsilanes

An efficient method for the B(C6F5)3-catalyzed allylation of secondary propargylic alcohol derivatives with allylsilanes has been developed. This method allows for the facile synthesis of a variety of 1,5-enynes in good to high yields with a number of functionalities, such as nitro, chloro, ester, and boronic ester, being tolerated under the reaction conditions

Catalytic Enantioselective Hydroboration of Cyclopropenes

2,2-Disubstituted cyclopropyl boronates have been synthesized with high degrees of diastereo- and enantioselectivity via the rhodium-catalyzed asymmetric hydroboration of 3,3-disubstituted cyclopropenes. A strong directing effect of ester and alkoxymethyl substituents has been demonstrated. The directing effect was found to be necessary in achieving high degrees of enantiomeric induction. Selected cyclopropylboronic derivatives were successfully employed in the Suzuki cross-coupling reaction to produce the corresponding optically active aryl- and vinylcyclopropanes in good yields

Highly Efficient B(C₆F₅)₃-Catalyzed Hydrosilylation of Olefins^†

A convenient and highly efficient method for the Lewis acid-catalyzed trans-selective hydrosilylation of alkenes has been developed. The mechanism of this novel protocol operates via direct addition of silylium type species across CC bond followed by trapping of the resultant carbenium ion with boron-bound hydride. A number of diversely substituted silanes possessing both aryl and alkyl groups at silicon atom were efficiently prepared using this hydrosilylation methodology. The possibility to employ aryl-containing hydrosilanes in this reaction opens broad capabilities for the synthesis of alcohols via a trans-selective hydrosilylation/Tamao−Fleming oxidation sequence, complementary to the existing cis-selective hydroboration/oxidation protocol

Catalytic Enantioselective Hydroboration of Cyclopropenes

2,2-Disubstituted cyclopropyl boronates have been synthesized with high degrees of diastereo- and enantioselectivity via the rhodium-catalyzed asymmetric hydroboration of 3,3-disubstituted cyclopropenes. A strong directing effect of ester and alkoxymethyl substituents has been demonstrated. The directing effect was found to be necessary in achieving high degrees of enantiomeric induction. Selected cyclopropylboronic derivatives were successfully employed in the Suzuki cross-coupling reaction to produce the corresponding optically active aryl- and vinylcyclopropanes in good yields

Transition Metal-Catalyzed Hydro-, Sila-, and Stannastannation of Cyclopropenes: Stereo- and Regioselective Approach toward Multisubstituted Cyclopropyl Synthons

The first highly efficient, stereo- and regioselective palladium-catalyzed hydro-, sila-, and stannastannation of cyclopropenes to give multisubstituted cyclopropylstannanes have been developed. It was shown that the addition across the double bond of cyclopropene is generally controlled by steric factors and proceeds from the least hindered face. The directing effect of alkoxymethyl substituents in the hydrostannation reaction of 3,3-disubstituted cyclopropenes was demonstrated. This methodology represents a powerful and atom-economic approach toward a wide variety of highly substituted cyclopropylstannanes, important building blocks unavailable by other methods