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Fig 1.

SpnF-mediated cyclization.

SpnF-mediated cyclization leading to cyclohexene ring in the biosynthesis of Spinosyn A.

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Fig 1 Expand

Fig 2.

Structural decomposition analysis of the cycloaddition reaction.

Structural decomposition analysis of the cycloaddition reaction involved in the biosynthesis of Spinosyn A into principal components (the atom numbering was the same as in compound 1 for comparative purpose).

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Table 1.

Calculated activation and reaction energies for the cycloaddition reactions.

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Table 1 Expand

Table 2.

Calculated activation barriers of Spinosyn A formation.

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Table 2 Expand

Fig 3.

Comparison of regular and proposed cycloaddition reactions.

Comparison of regular (black line) and proposed in the present study (blue line) cycloaddition reactions (calculated at the PM6 level). Coordination of amino acids and schematic substrate transformations are shown in the case of enzyme-catalyzed reaction (See S9 Fig and S10 Fig for structures and geometries).

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Fig 3 Expand

Fig 4.

Optimized molecular structure of transition state VIII-TS.

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Fig 4 Expand