Reaction Mechanism of Rh(I)-catalyzed Olefin Carboacylation:Enantioselectivity in the Formation of Chiral Poly-fused Rings†

doi:10.7503/cjcu20170405

Abstract

Abstract:

Density functional theory(DFT) methods were employed to investigate the reaction mechanisms of the formation of chiral poly-fused rings of benzocyclobutenone catalyzed by [Rh(R,R-DIOP)]⁺ in gas phase, THF and water. The theoretical results show that, the reaction system will proceed easily in gas phase, and the formation of the six-membered rings via TS2 is the rate-determining step, but the products are no distinct enantioselectivity. For the S- and R-channels in THF, the free energy barriers of C—C activation are elevated slightly from 79.5 and 69.3 kJ/mol to 80.2 and 88.8 kJ/mol, respectively, but do not alter the reaction characters. The coordination of Rh with the two C atoms is much weaker than that in gas phase, and the total free-energy barriers relative to the catalyst and the reactant in the S- and R-pathways are increased to 63.8 and 68.1 kJ/mol. For the S-channel, THF as solvent markedly increases the barrier via TS2 to 112.0 kJ/mol, and the process is still the rate-determining step. However, to the R-pathway, THF increases the barrier of forming the five-membered ring to 91.5 kJ/mol, but decreases the barrier via TS2 from 78.9 kJ/mol to 77.7 kJ/mol, so IM1→TS1 becomes the rate-determining step. When employing water as the solvent, the formation of the five-membered rings via TS1 becomes the rate-determining steps of these two reaction pathways, and the barriers of the S- and R-channels are 102.5 and 94.9 kJ/mol. As a result, solvents alter the rate-determining steps and their energy barriers of the reaction system. All these 3 methods predict that the R-pathway is the predominated reaction channel, but THF can evidently increase the enantioselectivity. The charge population was also analyzed by using the natural bond orbital(NBO) charges.

Key words: Olefin carboacylation, [Rh(R, R-DIOP)]+, Enantioselectivity, Poly-fused ring

CLC Number:

TrendMD:

CHENG Xueli, LI Yanfei, ZHAO Yanyun, LIU Yongjun. Reaction Mechanism of Rh(I)-catalyzed Olefin Carboacylation:Enantioselectivity in the Formation of Chiral Poly-fused Rings^†[J]. Chem. J. Chinese Universities, 2018, 39(3): 521.

Figures/Tables 8

Scheme 1 Formation of poly-fused rings from benzocyclobutenone derivatives catalyzed by [Rh(R,R-DIOP)]+The Arabic numerals besides atoms are the selected atomic sequence numbers.

Fig.1 Optimized structures of S-R, R-R and their corresponding products obtained by BP86 functionals in gas phase and in THF(in brackets) as well as by M06-2X in THF(in square brackets)Bond lengths are in nm.

Fig.2 Gibbs free energy profiles obtained by BP86 functional in gas phase(A) and M06-2X functionals in THF(B)The S-R→S,R-P reaction channel are drawn in solid lines, and R-R→R,R-P channel are in dash lines.

Fig.3 Intermediates and transition states of the C—C activation in the S- and R-channels optimized at BP86/6-31G(d,p) and M062X/6-31G(d,p)//PCM levelGeometrical structures are drawn on the basis of gas-phase skeletons, and the structural parameters obtained by M062X in THF are shown in brackets. Bond lengths are in nm.

Fig.4 Intermediates and transition states in the S- and R-cyclization channels optimized at BP86/6-31G(d,p) and M062X/6-31G(d,p)//PCM level Structural parameters obtained by M062X in THF are shown in brackets. Bond lengths are in nm.

Fig.5 Gibbs free energy profiles in kJ/mol obtained by M06-2X functionals in waterThe S-R→S,R-P reaction channel are drawn in solid lines, and R-R→R,R-P channel are in dash lines.

Fig.6 Optimized structural parameters of the intermediates and transition states in the S-R→S,R-P and R-R→R,R-P reaction channels at M062X/6-31G(d,p)//PCM level in waterBond lengths are in nm.

Table 1 Selected NBO charges for O1, C2, C3, C4 and C5 acquired from 3 DFT functionals

Species	BP86 in gas phase					M06-2X in THF					M06-2X in water
Species	O1	C2	C3	C4	C5	O1	C2	C3	C4	C5	O1	C2	C3	C4	C5
S-IM0	-0.462	-0.243	-0.271	-0.475	0.560	-0.537	-0.255	-0.275	-0.480	0.637	-0.525	-0.319	-0.276	-0.451	0.629
S-TS0	-0.517	-0.232	-0.264	-0.453	0.515	-0.571	-0.254	-0.249	-0.438	0.627	-0.556	-0.271	-0.266	-0.430	0.620
S-IM1	-0.514	-0.168	-0.259	-0.483	0.574	-0.574	-0.192	-0.253	-0.451	0.639	-0.577	-0.198	-0.269	-0.442	0.598
S-TS1	-0.505	-0.147	-0.220	-0.526	0.600	-0.561	-0.178	-0.185	-0.526	0.688	-0.563	-0.177	-0.183	-0.524	0.684
S-IM2	-0.487	-0.092	-0.324	-0.574	0.570	-0.550	-0.104	-0.320	-0.565	0.625	-0.555	-0.102	-0.320	-0.564	0.613
S-TS2	-0.492	-0.092	-0.316	-0.586	0.500	-0.555	-0.096	-0.314	-0.599	0.577	-0.559	-0.095	-0.310	-0.615	0.570
S-IM3	-0.492	-0.093	-0.303	-0.526	0.483	-0.552	-0.100	-0.300	-0.579	0.594	-0.561	-0.099	-0.298	-0.562	0.652
R-IM0	-0.476	-0.231	-0.271	-0.483	0.561	-0.540	-0.259	-0.263	-0.459	0.645	-0.529	-0.307	-0.278	-0.445	0.627
R-TS0	-0.510	-0.231	-0.262	-0.446	0.514	-0.566	-0.248	-0.239	-0.441	0.629	-0.552	-0.282	-0.261	-0.433	0.614
R-IM1	-0.509	-0.173	-0.262	-0.484	0.564	-0.575	-0.197	-0.261	-0.447	0.595	-0.577	-0.195	-0.267	-0.441	0.598
R-TS1	-0.500	-0.152	-0.219	-0.530	0.600	-0.558	-0.179	-0.184	-0.521	0.688	-0.560	-0.179	-0.182	-0.519	0.684
R -IM2	-0.492	-0.090	-0.325	-0.578	0.567	-0.554	-0.100	-0.318	-0.568	0.624	-0.558	-0.098	-0.318	-0.566	0.617
R-TS2	-0.490	-0.093	-0.318	-0.587	0.501	-0.553	-0.099	-0.311	-0.615	0.581	-0.558	-0.099	-0.310	-0.620	0.567
R-IM3	-0.489	-0.096	-0.305	-0.524	0.482	-0.551	-0.103	-0.303	-0.560	0.590	-0.559	-0.102	-0.300	-0.565	0.652

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