Transition Metal‐Free Vinylcyclopropanation of Olefins via Carbolithiation Reactions: Synthesis of 3‐Azabicyclo[3.1.0]hexanes

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N-allyl N-(3-alkoxymethyl-2-lithioallyl) amines act as carbenoid equivalents in a transition metal-free tandem 5-exo carbolithiation/3-exo SN' reaction to synthesize 1-vinylazabicyclo[3.1.0]hexanes with high diastereoselectivity. Novelty: ClaimNovelty.METHODOLOGICAL. Consensus alignment: ConsensusAlignment.NEUTRAL.

Nuria Cases; Marta Solas; M. Pilar Castroviejo; Samuel Suárez‐Pantiga; Miguel A. Rodrı́guez; Roberto Sanz

doi:10.1002/adsc.70724

August 20, 2026Advanced Synthesis & CatalysisOpen Access

Transition Metal‐Free Vinylcyclopropanation of Olefins via Carbolithiation Reactions: Synthesis of 3‐Azabicyclo[3.1.0]hexanes

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Key Points

To develop a transition metal-free vinylcyclopropanation protocol for the synthesis of functionalized 1-vinyl-3-azabicyclo[3.1.0]hexanes using carbenoid equivalents.
Utilized N-allyl N-(3-alkoxymethyl-2-lithioallyl) amines in a tandem 5-exo carbolithiation and 3-exo SN' cyclization pathway.
Introduced diverse substituents at multiple positions of the azabicyclic scaffold to assess substrate scope and diastereoselectivity.
Conducted density functional theory (DFT) computational calculations to determine the energetic profiles and transition-state geometries.
Constructed 1-vinyl-3-azabicyclo[3.1.0]hexanes in the absence of transition metals via an efficient tandem cyclization process.
Obtained high diastereoselectivities across most substituted positions of the azabicyclic ring system.
DFT modeling uncovered alternative transition states that account for stereochemical outcomes that diverge from standard chair-like pathways.

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Implication

Mechanistic synthetic study demonstrates transition metal-free vinylcyclopropanation yielding 1-vinylazabicyclo[3.1.0]hexanes with high diastereoselectivity, indicating versatile heterocyclic...

Abstract

A formal vinylcyclopropanation of olefins from N ‐allyl N ‐(3‐alkoxymethyl‐2‐lithioallyl) amines acting as carbenoid equivalents is described. The reaction proceeds through a tandem 5‐ exo carbolithiation/3‐ exo S N ʹ affording 1‐vinylazabicyclo[3.1.0]hexanes. Different substituents can be located at any of the other positions of the azabicycle, leading in most cases to high diastereoselectivities. DFT studies have been performed to account for the observed stereoselectivities that could not be rationalized in all cases through the expected chair‐like transition states.

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Cases et al. (2026) studied this question.

synapsesocial.com/papers/6a89600eca7ade938187f1c0 https://doi.org/10.1002/adsc.70724

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Transition Metal‐Free Vinylcyclopropanation of Olefins via Carbolithiation Reactions: Synthesis of 3‐Azabicyclo[3.1.0]hexanes

Key Points

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Implication

Abstract

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Transition Metal‐Free Vinylcyclopropanation of Olefins via Carbolithiation Reactions: Synthesis of 3‐Azabicyclo[3.1.0]hexanes

Key Points

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Implication

Abstract

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