S1

Supporting Information

Synthesis and Application of A New

Hexamethyl-1,1’-spirobiindane-based Chiral Bisphosphine

(HMSI-PHOS) Ligand in Asymmetric Allylic Alkylation

Shirui Chang, Lei Wang and Xufeng Lin*

Laboratory of Asymmetric Catalysis and Synthesis, Department of Chemistry,

Zhejiang University, Hangzhou 310027, China

E-mail: lxfok@zju.edu.cn

Table of Contents

1. Copies of NMR spectra……………..........................................……………....… S2

2. Copies of HPLC trace……………………………………………………………S30

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2018

S2

Copies of NMR spectra 3,3,3',3',5,5'-hexamethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-6,6'-diol (5)

S3

7,7'-dibromo-3,3,3',3',5,5'-hexamethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-6,6'-diol (6)

S4

(R)-7,7'-dibromo-3,3,3',3',5,5'-hexamethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-6,6'-diyl (2S,2'S)-bis(2-(6-methoxynaphthalen-2-yl)propanoate) (Ra,S,S)-7

S5

(S)-7,7'-dibromo-3,3,3',3',5,5'-hexamethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-6,6'-diyl (2S,2'S)-bis(2-(6-methoxynaphthalen-2-yl)propanoate) (Sa,S,S)-7

O

O

BrBr

O

O

O

O

O

O

BrBr

O

O

O

O

S6

(R)-7,7'-dibromo-3,3,3',3',5,5'-hexamethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-6,6'-diyl bis(trifluoromethanesulfonate) (R)-8

OTf

OTf

BrBr

OTf

OTf

BrBr

S7

(R)-7,7'-dibromo-3,3,3',3',5,5'-hexamethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene] (R)-9

S8

(R)-(3,3,3',3',5,5'-hexamethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-7,7'-diyl)bis(diphenylphosphane) (R)-1a

S9

S10

(R)-(3,3,3',3',7,7'-hexamethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,5'-diyl)bis(di-p-tolylphosphane) (R)-1b

S11

(R)-(3,3,3',3',5,5'-hexamethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-7,7'-diyl)bis(bis(3,4-dimethylphenyl)phosphane) (R)-1c

S12

PAr2PAr2

Ar=3,4-(CH3)2C6H4

S13

(R)-(3,3,3',3',5,5'-hexamethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-7,7'-diyl)bis(bis(4-(trifluoromethyl)phenyl)phosphane) (R)-1d

S14

S15

Diethyl (R,E)-2-(1,3-bis(4-chlorophenyl)allyl)malonate (4a)

S16

Dimethyl (R,E)-2-(1,3-bis(4-chlorophenyl)allyl)malonate (4b)

S17

Diisopropyl (R,E)-2-(1,3-bis(4-chlorophenyl)allyl)malonate (4c)

S18

Dibenzyl (R,E)-2-(1,3-bis(4-chlorophenyl)allyl)malonate (4d)

S19

Dimethyl (S,E)-2-(1,3-bis(3-chlorophenyl)allyl)malonate (4e)

S20

Diethyl (S,E)-2-(1,3-bis(3-chlorophenyl)allyl)malonate (4f)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)

0102030405060708090100110120130140150160170180190f1 (ppm)

S21

Dimethyl (S,E)-2-(1,3-bis(2-chlorophenyl)allyl)malonate (4g)

S22

Diethyl (S,E)-2-(1,3-bis(2-chlorophenyl)allyl)malonate (4h)

102030405060708090100110120130140150160170f1 (ppm)

S23

Dibenzyl (S,E)-2-(1,3-bis(2-chlorophenyl)allyl)malonate (4i)

S24

Dimethyl (R,E)-2-(1,3-bis(4-bromophenyl)allyl)malonate (4j)

S25

Diethyl (R,E)-2-(1,3-bis(4-bromophenyl)allyl)malonate (4k)

O

O

O

O

Br Br

S26

Diisopropyl (R,E)-2-(1,3-bis(4-bromophenyl)allyl)malonate (4l)

S27

Dibenzyl (R,E)-2-(1,3-bis(4-bromophenyl)allyl)malonate (4m)

0.92

0.99

1.96

1.99

0.92

1.00

5.68

3.21

4.43

4.92

3.94

3.97

4.20

4.22

4.23

4.25

4.93

4.96

4.96

4.99

5.07

5.10

5.11

5.14

6.18

6.20

6.22

6.24

6.26

6.30

7.19

7.20

7.20

7.22

7.24

7.24

7.25

7.25

7.26

7.27

7.28

7.29

7.29

7.30

7.30

7.33

7.34

7.34

7.35

7.35

7.36

7.37

7.37

S28

Dimethyl (R,E)-2-(1,3-diphenylallyl)malonate (4n)

S29

Diethyl (R,E)-2-(1,3-di-p-tolylallyl)malonate (4o)

S30

Copies of HPLC trace Diethyl (R,E)-2-(1,3-bis(4-chlorophenyl)allyl)malonate (4a)

S31

Dimethyl (R,E)-2-(1,3-bis(4-chlorophenyl)allyl)malonate (4b)

S32

Diisopropyl (R,E)-2-(1,3-bis(4-chlorophenyl)allyl)malonate (4c)

S33

Dibenzyl (R,E)-2-(1,3-bis(4-chlorophenyl)allyl)malonate (4d)

S34

Dimethyl (S,E)-2-(1,3-bis(3-chlorophenyl)allyl)malonate (4e)

O

O

O

O

Cl Cl

S35

Diethyl (S,E)-2-(1,3-bis(3-chlorophenyl)allyl)malonate (4f)

S36

Dimethyl (S,E)-2-(1,3-bis(2-chlorophenyl)allyl)malonate (4g)

S37

Diethyl (S,E)-2-(1,3-bis(2-chlorophenyl)allyl)malonate (4h)

S38

Dibenzyl (S,E)-2-(1,3-bis(2-chlorophenyl)allyl)malonate (4i)

S39

Dimethyl (S,E)-2-(1,3-bis(4-bromophenyl)allyl)malonate (4j)

S40

Diethyl (R,E)-2-(1,3-bis(4-bromophenyl)allyl)malonate (4k)

O

O

O

O

Br Br

O

O

O

O

Br Br

S41

Diisopropyl (R,E)-2-(1,3-bis(4-bromophenyl)allyl)malonate (4l)

O

O

O

O

Br Br

S42

Dibenzyl (R,E)-2-(1,3-bis(4-bromophenyl)allyl)malonate (4m)

O

O

O

OBnBn

Br Br

S43

Dimethyl (R,E)-2-(1,3-diphenylallyl)malonate (4n)

S44

Diethyl (R,E)-2-(1,3-di-p-tolylallyl)malonate (4o)

O

O

O

O