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. 2020 Jul 8;11(30):7950-7956.
doi: 10.1039/d0sc02054k.

Nickel-catalyzed three-component olefin reductive dicarbofunctionalization to access alkylborates

Xiao-Xu Wang  1 , Xi Lu  1 , Shi-Jiang He  1 , Yao Fu  1
Affiliations

Nickel-catalyzed three-component olefin reductive dicarbofunctionalization to access alkylborates

Xiao-Xu Wang et al. Chem Sci. .

Abstract

We report a three-component olefin reductive dicarbofunctionalization for constructing alkylborates, specifically, nickel-catalyzed reductive dialkylation and alkylarylation of vinyl boronates with a variety of alkyl bromides and aryl iodides. This reaction exhibits good coupling efficiency and excellent functional group compatibility, providing convenient access to the late-stage modification of complex natural products and drug molecules. Combined with alkylborate transformations, this reaction could also find applications in the modular and convergent synthesis of complex compounds.

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Conflict of interest statement

There is no conflict of interest to report.

Figures

Scheme 1
Scheme 1. Dicarbofunctionalization of vinyl boronates to access alkylborates. B2pin2 = bis(pinacolato)diboron. B2neop2 = bis(neopentyl glycolato)diboron. Tf = triflyl. Nu = nucleophile. E = electrophile. w = with. w/o = without. PC = photoredox catalysis. Ar = aryl. Alk = alkyl.
Scheme 2
Scheme 2. Substrate scope of primary alkyl bromides. Standard conditions: as shown in Table 1, entry 1, 0.2 mmol scale. Isolated yield. a The product was isolated after the oxidization of the corresponding alkylborate. Isolated yield. b Nuclear magnetic resonance (NMR) yield for the corresponding alkylborate. Dibromomethane was used as an internal standard.
Scheme 3
Scheme 3. Substrate scope of tertiary alkyl bromides. Standard conditions: as shown in Table 1, entry 1, 0.2 mmol scale. Isolated yield. PMP = p-methoxyphenyl.
Scheme 4
Scheme 4. Substrate scope of olefin reductive alkylarylation. Conditions: as shown in Table 1, entry 1, without NaI, 0.2 mmol scale. Isolated yield.
Scheme 5
Scheme 5. Synthetic applications. Standard conditions: as shown in Table 1, entry 1. Isolated yield. See the ESI for more details. NBS = N-bromosuccinimide. NIS = N-iodosuccinimide.
Scheme 6
Scheme 6. Mechanistic probes. Standard conditions: as shown in Table 1, entry 1, 0.2 mmol scale. Isolated yield. a GC yield. 4,4′-Dimethoxybenzophenone was used as an internal standard. See the ESI for more details. TDAE = tetrakis(dimethylamino)ethylene.
Scheme 7
Scheme 7. Envisioned mechanism. R1 = tert-alkyl. R2 = prim-alkyl or aryl. X = halogen.
See this image and copyright information in PMC

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