. Author manuscript; available in PMC: 2013 May 21.

Published in final edited form as: Angew Chem Int Ed Engl. 2012 Apr 5;51(21):5152–5156. doi: 10.1002/anie.201200035

Table 1.

Deoxypropionates by metallacycle-mediated alkyne–allylic alcohol cross-coupling and directed hydrogenation.



entry	alkyne	allylic alcohol	combined yield for coupling/deprotection (%)	1,4-diene	yield for conversion to deoxypropionate (%)	deoxypropionate
1			50^a		80^c
2			60^a		82^c
3			50^a		82^c
4			56^a		80^c
5			62^a		79^c
6			72^b		87^c

Reaction conditions:

^a)

For Ti-mediated reductive cross-coupling: ClTi(Oi-Pr)₃, c-C₅H₉MgCl, PhMe, Et₂O; For global desilylation: TBAF, HMPA, 35 °C.

^b)

Mono desilylation: TBAF, THF.

^c)

Rh[nbd(dppb)]BF₄, CH₂Cl₂, H₂ (500 psi) – reactions were typically run using 30 mol% of the Rh-catalyst; similar yields were observed when catalyst loading was reduced to 10 mol%. See Supporting Information for experimental details.