FULL PAPER
10.50 major (s, 1 H, anti-cis-CH); 0.81–1.88 (m, 45 H, major and
Acknowledgments
minor adamantyl protons; ov. 3 H, allyl-CH3; ov. minor 1 H, anti-
cis-CH; ov. major 1 H, syn-cis-CH); 2.13 minor (s, 1 H, syn-cis-
CH); 2.42 major (d, JP,H = 17.2 Hz, 1 H, anti-trans-CH); 3.0 minor
(d, JP,H = 16.4 Hz, 1 H, anti-trans-CH); 3.82 major (d, JP,H = Hz12
1 H, syn-trans-CH); 4.03 minor (d, JP,H = 10.4 Hz, 1 H, syn-trans-
CH); 6.85–7.90 (m, 36 H, Ar) ppm. 13C{1H} NMR (100.6 MHz,
CDCl3): δ = 122.6 major (s, allyl-CH3); 30.8, 36.0 43.3 (s, C3, C4,
C2 Ad); 58.9 major (s, cis-CH2); 77.2 major (trans-CH2 ov. CDCl3);
78.5 (s, C1O Ad); 120.1–133.8 (C and CH Naph); 147.6 (s, COP);
151.9 (s, CO Ad) ppm. C94H88ClO6PPd: calcd. C 75.95, H 5.97;
found C 72.64, H 6.24. HR-MS/ESI: m/z calcd. 1449.5353 [M –
Cl]+; found 1449.5376.
The authors are thankful for the financial support from the Portug-
uese Fundação para a Ciência e a Tecnologia (FCT) (FCT/QREN/
FEDER/COMPETE - Programa Operacional Fatores de Competi-
tividade, grant number PTDC/QUI-QUI/112913/2009 and PhD
grant SFRH/BD/60499/2009, to R. M. B. C.) and from the Spanish
Ministerio de Economía y Competitividad (MINECO), grant
number CTQ2010-15292/BQU.
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Chloro(η3-2-Me-allyl){tris[(R)-2Ј-(1-adamantyl ester)-1,1Ј-bi-
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0.05 mmol) and 5 (144 mg, 0.105 mmol), the title product was ob-
tained as a white solid, yield 109 mg (70%). Isomer ratio observed
in solution 2.5:1. 31P{1H} NMR (121 MHz, CDCl3): δ = 1118.0
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1
(major), 118.86 (minor) ppm. H NMR (400.1 MHz, CDCl3): δ =
10.85 major (s, 1 H, anti-cis CH); 1.14 major (s, 3 H, allyl-CH3);
1.23–1.78 (m, 45 H, major and minor adamantyl protons; ov.
minor 1 H, anti-cis CH; ov. minor 3 H, allyl-CH3; ov. major and
minor 1 H, syn-cis CH); 1.87 major (d, JP,H = 16 Hz, 1 H, anti-
trans-CH); 3.13 minor (d, JP,H = 16 Hz, 1 H, anti-trans-CH); 3.86
major (d, JP,H = 12.0 Hz, 1 H, syn-trans-CH); 4.29 minor (d, JP,H
= 12.0 Hz, 1 H, syn-trans-CH); 6.73–7.90 (m, 36 H, Ar) ppm.
13C{1H} NMR (100.5 MHz, CDCl3): δ = 122.7 major (s, allyl-
CH3); 27.6, 36.1, 37.9, 40.5 (s, C3, C4, C2, C1 Ad); 57.4 major (s,
cis-CH2); 80.7 major (d, JP,C = 50 Hz, trans-CH2); 118.8–133.4 (s,
C and CH Binaph); 146.9 (s, COP); 147.0 (s, CO Ad); 175.6 (s,
COO) ppm. C97H88ClO9PPd: calcd. C 74.18, H 5.65; found C
74.19, H 6.50. HR-MS/ESI: m/z calcd. 1533.5201 [M – Cl]+; found
1533.5214.
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General Procedure for Asymmetric Hydrovinylation: Hydrovinyl-
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with an external jacket connected to an ethanol bath and tempera-
ture controlled using a thermostat to Ϯ0.5 °C. The internal tem-
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of the chosen neutral complex Pd1–Pd5, styrene (20 mmol) and
AgBF4 (1.1 molar equiv.) with respect to the amount of Pd were
dissolved in dichloromethane (15 mL) and stirred for 10 min shel-
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solution was placed by syringe into the autoclave, which had been
purged by successive vacuum/nitrogen cycles and thermostatted to
25 °C. Ethylene was admitted until a pressure of 16 bar was
reached. After the selected time, the autoclave was slowly de-
pressurised and a 10% aqueous NH4Cl solution (10 mL) was
added. The mixture was stirred for 10 min to quench the catalyst.
The organic layer was separated, dried with Na2SO4, filtered
through a plug of SiO2 and subjected to GC analysis to determine
the distribution of the products and the enantiomeric excess with
30 m Agilent HP 5 and Astec Chiraldex DM columns.
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General Procedure for Asymmetric Hydrogenation: A solution of
[Rh(cod)2]BF4 or [Rh(cod)2]OTf (0.015 mmol) and the mono-
phosphite (0.03 mmol) in dry CH2Cl2 (4 mL) was introduced into a
stainless-steel autoclave and stirred for 10 min. Dimethyl itaconate
(1.5 mmol) was added with a cannula and the autoclave was then
filled with the desired hydrogen pressure. After 24 h (or 48 h), the
autoclave was opened and the reaction mixture was concentrated
to dryness, dissolved in n-hexane and passed over a silica gel pad.
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