An Investigation of the Enolization and Isomeric Products Distribution in the Water Promoted Aldol Reaction of Tropinone and Granatanone

Table 6

Calculated (B3LYP/6-31g(d) CPCM) reaction parameters for granatanone enol addition to aldehydes.

R^1	Reaction medium		Aldol isomer		HB-O		k(anti)/k(syn)		HB-O			K anti/syn HB-O	HB-N		K anti/syn HB-N	anti/syn
Ph	Gas/neat		exo,syn-4a		21.0		18.1		–1.3			56.8	–5.5		0.1	0.12
			exo,anti-4a		19.3				–3.7				–4.0
	Water		exo,syn-4a		21.6		7.5		–1.2			26.6	–5.8		0.6	0.64
			exo,anti-4a		20.4				–3.2				–5.5
p-NO2-C6H4	Gas/neat		exo,syn-4b		18.1		5.3		–5.2			20.2	–9.0		0.2	0.25
			exo,anti-4b		17.1				–7.0				–7.9
	Water		exo,syn-4b		18.3		3.0		–5.5			10.6	–10.2		0.7	0.96
			exo,anti-4b		17.7				–6.9				–10.0
p-F-C6H4	Gas/neat		exo,syn-4c		20.8		20.3		–0.9			49.7	–5.3		0.1	0.22
			exo,anti-4c		19.0				–3.3				–4.1
	Water		exo,syn-4c		20.9		6.8		–1.5			31.7	–6.5		0.6	0.82
			exo,anti-4c		19.8				–3.6				–6.2
p-Cl-C6H4	Gas/neat		exo,syn-4d		19.9		10.4		–2.1			48.8	–6.6		0.3	0.20
			exo,anti-4d		18.5				–4.4				–5.9
	Water		exo,syn-4d		20.5		0.7		–2.5			15.2	–7.2		1.2	0.82
			exo,anti-4d		20.7				–4.1				–7.3
p-CF3-C6H4	Gas/neat		exo,syn-4e		18.9		4.7		–3.4			20.0	–7.6		0.2	0.25
			exo,anti-4e		18.0				–5.1				–6.6
	Water		exo,syn-4e		19.3		2.8		–3.6			11.4	–9.2		0.4	0.20
			exo,anti-4e		18.6				–5.0				–8.6
m-MeO-C6H4	Gas/neat		exo,syn-4f		20.8		18.3		–1.3			61.4	–5.9		0.1	0.11
			exo,anti-4f		19.1				–3.8				–4.7
	Water		exo,syn-4f		21.1		6.4		–1.8			14.6	–6.4		1.0	0.64
			exo,anti-4f		20.0				–3.4				–6.4
-Naphth-	Gas/neat		exo,syn-4g		21.9		14.2		0.8			135.6	–5.7		0.04	0.02
			exo,anti-4g		20.3				–2.1				–3.8
	Water		exo,syn-4g		21.1		3.4		–0.4			82.1	–7.2		0.3	0.54
			exo,anti-4g		20.4				–3.0				–6.6
p-MeO-C6H4	Gas/neat		exo,syn-4h		22.2		25.7		0.8			47.3	–3.4		0.3	n.d.
			exo,anti-4h		20.3				–1.5				–2.7
	Water		exo,syn-4h		22.6		14.5		0.4			26.2	–3.9		1.5	n.d.
			exo,anti-4h		21.0				–1.5				–4.2
MAD HBN															41.3